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Camerino, Italy
31 August-04 September 2019
Summer School
Organometallic Chemistry: New Directions and Perspectives
Interdivisional Group of Organometallic Chemistry
University of Camerino
School of Pharmacy and School of Science and Technology
12th International School of Organometallic Chemistry
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Title Organometallic Chemistry: New Directions and Perspectives ISBN 9788867680412 e-printed by University of Camerino – e-mail: [email protected] 26 August 2019
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Organometallic Chemistry: New Directions and Perspectives
The ISOC series is the most important school on organometallic chemistry at the European level,
organized by Camerino University under the auspices of EuCheMS (the European Association for
Chemical and Molecular Sciences) and the Interdivisional Group of Organometallic chemistry of the
Italian Chemical Society. The aim is to encourage the presence of young researchers and Ph.D
students both from University and Industry, including those not directly involved in organometallic
research projects, in order to bring together young researchers and distinguished European scientists
as a contribution to the important goal of increasing the transfer of knowledge at a high level between
different European countries and different generation of scientists. The 12th edition of ISOC will deal
with fundamental principles to their use in novel applications, with a specific focus on the role of
organometallic chemistry in finding solutions to many of the major societal challenges in the 21st
century: from the development of sustainable energy solutions to the mitigation of climate change,
from the synthesis of effective therapeutics to the production of new materials ranging from novel
polymers to nanomaterials, from the generation of industrial feedstocks to the remediation of the
environment. The scientific community is increasingly being stimulated to tackle problems of
practical interest and the society will undoubtedly rely on advances made in the field of
organometallic chemistry.
INTRODUCTION
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Saturday 31 August Sunday 1 September Monday 2 September Tuesday 3 September Wednesday 4 September
7:45-8:45 Breakfast
7:45-8:45 Breakfast
7:30-8:15 Breakfast
7:45-8:45 Breakfast
9:00-15:00 Registration
9:00-10:30 Prof. Lutz Ackermann Sustainable C–H Activation from Late-Step Peptide Diversification to Electrocatalysis
9:00-10:30 Prof. Simon Woodward Organometallic Catalysis for New Molecular Architectures
8:30-10:00 Prof. Lukas Gooßen Decarboxylative coupling reactions: A modern strategy for C–C and C–heteratom bond formation
9:00-10:30 Prof. Eduardo Peris Supramolecular Interactions in Polyaromatic N-Heterocyclic Carbenes. Host Guest Chemistry Properties and Catalytic Implications
15:30-16:00 Opening Ceremony
10:30-11:00 Coffee Break
10:30-11:00 Coffee Break
10:00-11:30 Prof. Anny Jutand Contribution of Electrochemistry to Organometallic Catalysis
10:30-10:45 Coffee Break
11:00-12:30 Prof. Maria Conception Gimeno Synthesis and Applications of Novel Organogold Complexes
11:00-12:30 Prof. Angela Casini Exploiting Organometallic Chemistry for Biomedical Applications
11:30-11:45 Coffee Break
10:45-12:15 Prof. Maurizio Taddei Metal Catalysed Hydrogen Transfer and Hydrogen Addition Reactions for the Synthesis of Active Pharmaceutical Ingredients
11:45-13:15 Prof. Manuel Alcarazo Synthetic Applications of Cationic Phosphines, Arsines and Sulfides
16:00-17:30 Prof. Bao N. Nguyen Homogeneous Catalysis: From Academia to Industry
12:30-14:30 Lunch
12:30-14:30 Lunch
13.15-15:00 Lunch
12:15-13:00 Closing Ceremony
17:30-19:00 Prof. Emma Gallo Aziridination of Alkenes Catalysed by Iron and Ruthenium Complexes
14:30-16:00 Prof. Jonathan A. Gareth Williams Light-Emitting Organometallic Complexes: From Design Principles and Excited States to Applications in Oleds and Bio-Imaging
14:30-16:00 Prof. Jerome Lacour Selective Synthesis and Catalysis via Diazo Decomposition Reactions and Reactive Metal Carbenes
15:15-20:00 Social Tour
13:00-15:00 Lunch
16:00-17:30: Prof. Olivier Baudoin Palladium (0)-catalyzed C(sp3)-H activation: from method development to natural product synthesis
19:00 Welcome Cocktail
16:00-17:00 Flash-presentations
17:30-18:30 Flash-presentations
20:30 Social Dinner
17:00-19:00 Coffee Break with Poster Session
18:30-20:00 Coffee Break with Poster Session
20:00 Welcome Dinner
20:00 Dinner
TIMETABLE
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Saturday, 31 August: 15.30: Opening Session 16.00: Prof. Bao N. Nguyen “Homogeneous Catalysis: From Academia to Industry” 17.30: Prof. Emma Gallo “Aziridination of Alkenes Catalysed by Iron and Ruthenium Complexes” 20.00: Welcome Cocktail
Sunday, 1 September: 09.00: Prof. Lutz Ackermann “Sustainable C–H Activation from Late-Step Peptide Diversification to Electrocatalysis” 10.30: Coffee break 11.00: Prof. Maria Conception Gimeno “Synthesis and Applications of Novel Organogold Complexes” 12.30: Lunch 14.30: Prof. Jonathan A. Gareth Williams “Light-Emitting Organometallic Complexes: from Design Principles and Excited States to Applications in Oleds and Bio-Imaging” 16.00: Flash Presentation 17.00: Coffee break with Poster session 20.00: Dinner
Monday, 2 September: 09.00: Prof. Simon Woodward “Organometallic Catalysis for New Molecular Architectures” 10.30: Coffee break 11.00: Prof. Angela Casini “Exploiting Organometallic Chemistry for Biomedical Applications” 12.30: Lunch 14.30: Prof. Jerome Lacour “Selective Synthesis and Catalysis via Diazo Decomposition Reactions and Reactive Metal Carbenes” 16.00: Prof. Olivier Baudoin “Palladium (0)-Catalyzed C(Sp3)-H Activation: from Method Development to Natural Product Synthesis” 17.30: Flash Presentation 18.30: Coffee break with Poster session 20.00: Dinner
Tuesday, 3 September: 08.30: Prof. Lukas Gooßen “Decarboxylative Coupling Reactions: a Modern Strategy for C–C and C–Heteratom Bond Formation” 10.00: Prof Anny Jutand “Contribution of Electrochemistry to Organometallic Catalysis” 11.30: Coffee break 11.45: Prof. Manuel Alcarazo “Synthetic Applications of Cationic Phosphines, Arsines and Sulfides” 13.15: Lunch 15.15: Social Tour 20.30: Social dinner
Wednesday, 4 September: 08.30: Prof Eduardo Peris “Supramolecular Interactions in Polyaromatic N-Heterocyclic Carbenes. Host-Guest Chemistry Properties and Catalytic Implications” 11.30: Coffee break 10.45: Prof. Maurizio Taddei “Metal Catalysed Hydrogen Transfer and Hydrogen Addition Reactions for the Synthesis of Active Pharmaceutical Ingredients” 12.15: Prizes and Closing Ceremony 13.00: Lunch
TIMETABLE
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Prof. Augusto Cingolani Prof. Claudio Pettinari Prof. Fabio Marchetti Prof. Riccardo Pettinari
Honorary President of ISOC Chair Co-chair
Dr. Corrado Di Nicola Prof. Marino Petrini Prof. Enrico Marcantoni Prof. Alessandro Palmieri
Dr. Serena Gabrielli Dr. Alessia Tombesi
Advisory Board Scientific Committee
Prof. Pierre Braunstein - University of Strasbourg, France Prof. Ernesto Carmona - University of Sevilla, Spain Prof. Jan Čermák - Institute of Chemical Process Fundamentals - Czech Republic Prof. Paul Dyson – EPLF Lausanne, Switzerland Prof. Kees Elsevier - University of Amsterdam, Netherlands
Prof. Roberto Gobetto - University of Torino, Italy Prof. Helena Grennberg - Uppsala University, Sweden Prof. Hansjörg Grützmacher - ETH Zurich, Switzerland
Prof. Alceo Macchioni - University of Perugia, Italy
Prof. Jacques Maddaluno – CNRS Paris, France Prof. David Milstein - The Weizmann Institute of Science, Israel Prof. Eduardo Peris Fajarnés - University of Jaume-I, Spain
Prof. Robin A. Perutz - University of York, United Kingdom Prof. Maurizio Peruzzini - ICCOM CNR Firenze, Italy Prof. Claudio Pettinari - University of Camerino, Italy
Prof. Rinaldo Poli - LCC-CNRS Toulouse, France Prof. Armando Pombeiro - University of Lisbon, Portugal Prof. Fabio Ragaini - University of Milan, Italy Prof. Gianna Reginato - ICCOM CNR Firenze, Italy
Prof. Michelangelo Scalone - F. Hoffmann - La Roche AG
Prof. Michelangelo Scalone - F. Hoffmann - La Roche AG Prof. Valerio Zanotti - University of Bologna, Italy
Prof. Walter Baratta
Prof. Andrea Biffis
Prof. Piergiorgio Cozzi
Prof. Enrico Marcantoni
Prof. Carlo Nervi
Prof. Francesco Paolo Fanizzi
Prof. Gianluca Farinola
Prof. Claudio Pettinari
Prof. Fabio Ragaini
Prof. Gianna Reginato
Prof. Renata Riva
ORGANIZING COMMITTEE
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Prof. Lutz Ackermann
University of Goettingen “Sustainable C–H Activation from Late-Step Peptide Diversification to Electrocatalysis”
Biography: Prof. Lutz Ackermann studied Chemistry at the University Kiel, and performed his PhD with Prof. Alois Fürstner at the Max-PlankInstitut für Kohlenforschung. After a postdoctoral stay at UC Berkeley with Prof. Robert G. Bergman, he initiated his independent research career in 2003 at the Ludwig Maximilians-University München. In 2007, he became Full Professor at the Georg-August-University Göttingen. His recent awards and distinctions include an AstraZeneca Excellence in Chemistry Award, an ERC Grant and a Gottfried-Wilhelm-Leibniz-Preis. The development and application of novel concepts for sustainable catalysis constitutes his major current research interests, with a topical focus on C-H activation.
Prof. Manuel Alcarazo
University of Goettingen "Synthetic Applications of Cationic Phosphines, Arsines and Sulfides"
Biography: Prof. Manuel Alcarazostudied Chemistry at the of Seville, and performed his PhD with Prof. José M. Lassaletta at the Instituto de Investigaciones Químicas (CSIC) of Sevilla. After a postdoctoral stay at the Max-Planck-Institut für Kohlenforschung in Mülheim/Ruhr with Prof. Dr. Alois Fürstner, he initiated his independent research career in 2009 at the Max-Planck-Institut für Kohlenforschung in Mülheim/Ruhr. In 2015, he became Full Professor at the Georg-August-University Göttingen. Since 2017 is the Director of the Institute of Organic and Biomolecular Chemistry at the University of Göttingen.
Prof. Olivier Baudoin
University of Basilea "Palladium(0)-Catalyzed C(sp3)-H Activation: from Method Development to Natural Product Synthesis"
Biography: Prof. Olivier Baudoin studied Chemistry at the at Ecole Nationale Supérieure de Chimie de Paris, and performed his Master and doctoral studies under the supervision of Prof. Jean-Marie Lehn at the Collège de France in Paris. After a postdoctoral stay at the Scripps Research Institute, La Jolla, USA under the supervision of Prof. K. C. Nicolaou, he initiated his independent research career in 1999 at the Institut de Chimie des Substances Naturelles, Gif-sur-Yvette. In 2006, he became Full Professor at Université Claude Bernard Lyon 1. Since 2015 is Full Professor at the University of Basel.
SPEAKERS
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Prof. Angela Casini
University of Cardiff
“Exploiting Organometallic Chemistry for Biomedical Applications”
Biography: Prof. Angela Casini is Chair of Medicinal and Bioinorganic Chemistry at Cardiff University since 2015. She completed her PhD in Chemistry at the University of Florence in 2004, and, afterwards, moved to EPFL as senior scientist funded by the Swiss National Science Foundation. Between 2011-2015 she has been assistant professor at the University of Groningen, holding a Rosalind Franklin Fellowship, before taking up her current position at Cardiff University. She was awarded the 2012 European Medal for Biological Inorganic Chemistry and, in 2014, she has been listed by Thomson Reuters as one of the "World’s most influential scientific minds" in the field of Pharmacology. Since 2016 she is also Hans Fischer Senior Fellow of the prestigious Institute of Advanced Study of the Technical University of Munich. In 2018, she has been awarded the Burghausen Chemistry Diamond award, an acknowledgement of chemical and industrial innovation. Her research focuses on the study of the role of metal ions in biological systems and of the mechanisms of action of gold organometallic anticancer agents. Furthermore, novel applications for metal-based compounds and supramolecular coordination complexes are explored in various domains of chemical biology, drug delivery and physiology. In these fields, she is author of more than 200 publications.
Prof. Emma Gallo
University of Milan "Aziridination of Alkenes Catalysed by Iron and Ruthenium Complexes"
Biography: Prof. Emma Gallo received her PhD at the University of Lausanne in 1995 under the supervision of prof. Carlo Floriani. Then, she spent one year in Floriani’s Group as ‘Maitre Assistant’ before moving to University of Milano for a post-doctoral fellowship with prof. Sergio Cenini. She became Assistant Professor in 2001 and started her independent career in 2003 as Associate Professor at the Chemistry Department of Milano University. In 2007 she was Visiting Professor at the Pierre et Marie Curie - Paris VI University and in 2013 she received the National Academic Qualification as Full Professor. Her research is focused on: i) Synthesis of homogeneous catalyststo promote eco-compatible syntheses of fine chemicals by using organic azides and diazo-compounds as atom efficient nitrene and carbene transfer reagents. ii) Heterogenization of homogeneous catalystsin order to couple benefits of a ‘single-site’ catalysis with the easy recovery and recycle of the promoter. iii) Synthesis of chemosensors showing molecular structures which are suitable for detecting emerging pollutants in water by exploiting lock and key mechanisms.
Prof. J. A. Gareth Williams Durham University "Light-Emitting Organometallic Complexes: from Design Principles and Excited States to Applications in Oleds and Bio-Imaging"
Biography: Prof. J. A. Gareth was brought up on the island of Anglesey in Wales. He studied Chemistry at the University of Oxford, before moving to Durham University to work towards his PhD with Prof. David Parker, on the synthesis and luminescence properties of macrocyclic metal complexes. After post-doctoral work with Prof. Jean-Pierre Sauvage in Strasbourg, he returned to Durham where he is currently a Professor of Chemistry. His main research interests are currently in the synthesis, excited-state properties, and applications of a variety of organometallic and coordination complexes, and the bacteriostatic action of aza-carboxylate ligands.
SPEAKERS
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Prof. Anny Jutand. École normale supérieure, PSL University, Sorbonne Université, CNRS "Contribution of Electrochemistry to Organometallic Catalysis"
Biography: Prof. Anny Jutand studied Chemistry at the Ecole Nationale Supérieure de Chimie in Paris and received her PhD in 1980 at the University Paris XIII (advisor: Prof. J. F. Fauvarque), developing palladium-catalyzed arylations of Grignard reagents and zinc enolates. After a post-doctoral position at the Royal Institute of Technology in Stockholm, Sweden (advisor: Prof. B. Åkermark) she went back to University Paris XIII where she developed nickel-catalyzed electrosynthesis of anti-inflammatory agents (ibuprofen, naproxen…). Then, she joined Dr. C. Amatore' s group at the Ecole Normale Superieure in Paris where she used electrochemical techniques to investigate the mechanisms of catalytic reactions. She became Director of Research at CNRS in 1992. Research interests: Mechanistic studies on transition metal-catalyzed reactions (Pd, Ni, Cu, Fe, Ru, Rh). Activation of organic molecules by transition metal complexes and by electron transfer. Synthetic development and mechanism. She received in 2003: the award of the Organic Chemistry Division of the French Chemical Society, in 2008: the Grand Prix d’Etat of the French Academy of Sciences in 2018: thePrix Achille Le Bel of the French Chemical Society.
Prof. Jerome Lacour University of Geneve "Selective Synthesis and Catalysis via Diazo Decomposition Reactions and Reactive Metal Carbenes"
Biography: Prof. Jérôme Lacour was educated at the École Normale Supérieure in Paris. He holds an Agrégation in Physical Sciences and obtained in 1993 his Ph.D. in Chemistry at the University of Texas at Austin under the supervision of Prof. Philip D. Magnus. After post-doctoral studies in the laboratory of Prof. David A. Evans at Harvard University, he joined the Organic Chemistry Department of the University of Geneva in 1995. In 2001, he received the Sandoz Family Foundation professorship. Since 2004, he holds a full professor position in the department. Currently, his primary research interests are in asymmetric synthesis and catalysis using organic, physical organic, organometallic and coordination chemistry tools.
Prof. María Concepción Gimeno
Universidad de Zaragoza- CSIC "Synthesis and Applications of Novel Organogold Complexes"
Biography: Prof. M. Concepción Gimeno graduated in Chemistry at the University of Zaragoza and carried out the Ph.D. Thesis, under the supervision of Professors Rafael Usón and Antonio Laguna, at the same University. She carried out a postdoctoral stay at the University of Bristol with Prof. Gordon Stone, working on the synthesis and reactivity of transition metal carbines. In 1990 she obtained a position as Senior Scientist of the CSIC, in the Institute of Chemical Synthesis and Homogeneous Catalysis, and later, she got the promotion to Scientific Researcher in 2000 and Research Professor in 2008. Her scientific interests are focused on the design, study and analysis of new group 11 metal compounds with specific catalytic, luminescent and/or biological properties and with potential applications. She has been awarded with the IUPAC 2017 Distinguished Women in Chemistry and Chemical Engineering; the Excellence in Research of the Organometallic Chemistry Group (GEQO); in 2017, and the Excellence in Research of the Spanish Royal Society of Chemistry (RSEQ)” in 2018, among others.
SPEAKERS
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Prof. Lukas Gooßen Ruhr-University Bochum "Decarboxylative Coupling Reactions: a Modern Strategy for C–C and C–Heteratom Bond Formation"
Biography: Born 1969 in Bielefeld; 1989-1994 undergraduate studies in chemistry at the Universität Bielefeld / University of Michigan; 1994 research work with Prof. Dr. K. P. C. Vollhardt, University of California, Berkeley; 1994-1997 PhD. work with Prof. Dr. W. A. Herrmann, TU München; 1998 Postdoc with Prof. Dr. K. B. Sharpless, Scripps Research Institute; 1999-2000 research chemist at the Bayer AG (Central Research); 2000-2003 habilitation at the MPI für Kohlenforschung in the group of Prof. Dr. M. T. Reetz; 2003-2004 group leader at the MPI für Kohlenforschung; 2004-2005 Heisenberg fellow at the RWTH Aachen; 2005-2016 professor at the TU Kaiserslautern, 2008 visiting professor at the University of Toronto; since 2016 Evonik Chair of Organic Chemistry at the Ruhr-Universität Bochum.
Prof. Eduardo Peris University of Jaume I "Supramolecular Interactions in Polyaromatic N-Heterocyclic Carbenes. Host-Guest Chemistry Properties and Catalytic Implications"
Biography: Prof. Eduardo Peris graduated in Chemistry in 1988 in Valencia. He received his Ph.D. Degree in Chemistry in the Universidad de Valencia, under the supervision of Prof. Pascual Lahuerta. In 1994 he joined Robert Crabtree’s group at Yale University, where he stayed for two years, working on a research project regarding the determination of hydrogen bonding to metal hydrides. In October 1995 he moved to the Universitat Jaume I as an Assistant Professor, Lecturer and finally Professor of Inorganic Chemistry. At the Universitat Jaume I he started a research project related to the use of organometallic push-pull compounds with non-linear-optical properties. The current interest of his group is the design of new polytopic rigid N-heterocyclic carbene ligands (NHCs) that can be applied to the preparation of improved catalysts and advanced materials with attractive physical properties. In 2012 he was awarded the ‘Spanish Royal Society of Chemistry ’award in the field of Inorganic Chemistry Research. In September 2014, he was elected President of the Spanish Organometallic Chemistry Division, from the Spanish Royal Society of Chemistry.
Dr. Bao N. Nguyen University of Leeds "Homogeneous Catalysis: From Academia to Industry"
Biography: Dr. Bao Nguyen is a Lecturer in Physical Organic Chemistry at University of Leeds, where he has been from September 2012. He actively collaborates with colleagues from both the School of Chemistry and School of Chemical and Process Engineering to address current challenges in process chemistry. He is a core member of the Institute of Process Research and Development (iPRD), a flagship institute set up by the Leeds Transformation Fund. Dr Nguyen did his PhD in Organic Chemistry at the University of Oxford, under the supervision of Dr John M. Brown FRS. He then moved to Dr Michael C. Willis’ group, where he developed the first Pd-catalysed coupling reaction employing sulfur dioxide by suppressing catalyst deactivation. Afterward, he joined Imperial College London, working in Dr King Kuok Hii’s group to delineate the nature of the palladium species in different catalytic reactions and developing separation methods for these species. He was awarded his first independent position as a Ramsay Memorial Fellow at Department of Chemistry, Imperial College London.
SPEAKERS
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Prof. Maurizio Taddei University of Siena "Metal Catalysed Hydrogen Transfer and Hydrogen Addition Reactions for the Synthesis of Active Pharmaceutical Ingredients"
Biography: Maurizio Taddei obtained the doctoral degree in Chemistry in 1979 at the Department of Organic Chemistry of the University of Florence working with Prof. Alfredo Ricci. After a post-doc experience at University Chemical Laboratories in Cambridge (UK) with Prof. Ian Fleming, he became Research Assistant at the University of Florence in 1984 and Associate Professor at the Faculty of Agronomy of the University of Florence in 1992. In 1994 he became Professor of Organic Chemistry at the Faculty of Science at the University of Sassari and since 2001 he is Professor of Organic Chemistry at the Department of Biotechnology, Chemistry and Pharmacy of the University of Siena. He was recipient of the "G. Ciamician" silver medal in 1990, the “A. Mangini” gold medal in 2017 and the prize for Organic Synthesis and Methodology in 2012 from the Organic Chemistry Division of the Italian Chemical Society. He is author of more than 250 papers and 20 patents in the field of organic synthesis, bioorganic chemistry and medicinal chemistry. His fields of interest are natural product and biologically active product synthesis, development of high-throughput synthetic methodologies and chemical processes relevant in bio- and nano-medicine.
Prof. Simon Woodward University of Nottingham "Organometallic Catalysis For New Molecular Architectures"
Biography: Prof. Simon Woodward comes from a background encompassing the fusion of organic, organometallic and catalytic chemistry. After a PhD in the group of Prof Mark J Winter he undertook postdoctoral work in the groups of Prof M David Curtis and Dr John M Brown, FRS. Initially appointed to a Lectureship in Organometallic and Catalytic Chemistry at The University of Hull, he moved to a Readership in Organic Chemistry at the University of Nottingham. In 2006 he was promoted to a Personal Chair in Synthetic Organic Chemistry at Nottingham. He has over 145 publications in the areas of organic methodology, organometallic chemistry, electronic materials and selective/asymmetric catalysis. He has been director of both The European Ligand Bank and an International Marie Curie Ph.D. School in ‘catalysis of organic reactions’ encompassing the Universities of Nottingham, Geneva, Sassari and Dortmund. Recent developments involve new approaches to organic electronic materials and anti-cancer therapeutics.
SPEAKERS
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SPONSORS
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Homogeneous Catalysis: from Academia to Industry
Bao N. Nguyena*
Lecture 1, August 31, 16:00 a Institute of Process Research & Development, School of Chemistry, University of Leeds, West Yorkshire, LS2 9JT,
United Kingdom. [email protected]
White hundreds new catalytic reactions are reported in the highest impact journals each month, few of them
actually found wide-spread use in industrial context. This lecture discusses the required criteria for catalytic
reactions to be employed in production processes in chemical industry and the problems often encountered.
The underlying principles are exemplified in three case studies:
• Overcoming reversibility in enantioselective transfer hydrogenation1
• Developing a robust immobilised transfer hydrogenation catalyst2, 3
• Origin of high catalyst loading and poor reproducibility in Ullmann-Goldberg coupling4
[1] Sun, X., Gavriilidis, A. Org. Process Res. Dev. 2008, 12, 1218. [2] Lucas, S. J., Crossley, B. D., Pettman, A. J., Vassileiou, A. D., Screen, T. E. O., Blacker, A. J., McGowan, P. C. Chem.Commun. 2013, 5562. [3] Sherborne, G. J., Chapman, M. R., Blacker, A. J., Bourbe, R. A., Chamberlain, T. W., Crossley, B. D., Lucas, S. J., McGowan, P. C., Newton M. A., Screen, T. E. O., Thompson, P., Willans, C. E., Nguyen, B. N. J. Am. Chem. Soc., 2015, 137, 4151. [4] Sherborne, G. J., Adomeit, S., Menzel, R., Rabeah, J., Brückner, A., Fielding, M. R., Willans, C. E., Nguyen, B. N. Chem. Sci. 2017, 8, 7203.
LECTURES
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Aziridination of Alkenes Catalysed by Iron and Ruthenium Complexes
Emma Galloa*
Lecture 2, August 31, 17:30 a Department of Chemistry, University of Milan, Via C. Golgi 19, 20133 Milan (Italy).
Aziridines, the smallest N-heterocycle compounds, have attracted considerable attention in the last few
decades due to their many applications in biological and synthetic chemistry.1 Thanks to the energy associated
to the strained three-membered ring,2 the aziridine functionality is often responsible for the activity of
pharmaceutical species (such as antitumor compounds, antibiotics and enzyme inhibitors) as well as a
pronounced chemical reactivity. The striking chemical properties of aziridines render them useful building
blocks in the synthesis of several classes of fine-chemicals.3
In view of what stated above, the scientific community is constantly interested in developing efficient
procedures to introduce an aziridine moiety into organic skeletons and the one-pot reaction of an alkene double
bond with a nitrene [NR] source is a powerful synthetic strategy.
This lesson aims to provide an overview of the most important results, obtained during about last ten years,
on the catalytic activity of iron or ruthenium complexes to promote the catalytic aziridination of alkenes by
focusing a particular attention on innovative catalytic systems, which combine good performances with a good
eco-tolerability.4 The employment of iron derivatives is of noticeable importance due to the abundance of iron
metal on Earth as well as the low cost and low biological toxicity of iron-containing catalysts. Finally, the use
of iron and ruthenium porphyrins as efficient catalysts for mediating both the synthesis of aziridines and their
ring-opening reactions will be discussed.5
[1] Nikitjuka, A.; Jirgensons, A. Chem. Heterocycl. Compd. 2014, 49, 1544. [2] X.E. Hu, Tetrahedron 2004, 60, 2701. [3] Macha, L.; D'hooghe, M.; Ha, H.-J. Synthesis, 2019, 51,1491. [4] Damiano, C.; Intrieri, D.; Gallo, E. Inorg. Chim. Acta 2018, 470, 51. [5] a) D. Intrieri, D.M. Carminati, E. Gallo, Recent Advances in Metal Porphyrinoid-Catalyzed Nitrene and Carbene Transfer Reactions, in: K.M.S. Edited by Kadish, Kevin M.; Guilard, Roger (Ed.) Handbook of Porphyrin Science, World Scientific Publishing Co. Pte. Ltd., 2016, pp. 1-99. b) Intrieri, D.; Damiano, C.; Sonzini, P.; Gallo, E. J. Porphyrins Phthalocyanines 2019, 23, 305.
LECTURES
15
Sustainable C–H Activation from Late-Step Peptide Diversification to
Electrocatalysis
Lutz Ackermanna*
Lecture 3, September 1, 09:00 a Institute for Organic and Biomolecular Chemistry. Faculty of Chemistry, University of Göttingen, Tammannstr 2,
Göttingen 37077, Germany. [email protected]
C–H activation has surfaced as a powerful platform in molecular synthesis, with transformative applications
to material sciences and drug discovery, among others.1
In this context, we have introduced carboxylates, for position-selective C–H arylations and alkylations
with versatile ruthenium(II) complexes,2 displaying complementary selectivities as compared to nickel, cobalt,
iron, copper or manganese catalysis.3 Detailed mechanistic insights into the working mode of the key C–H
ruthenation step set the stage for ruthenium(II)-catalyzed twofold C–H functionalizations as well as step-
economical oxidative alkyne annulations.4 The oxidative C–H functionalization strategy enabled
ruthenium(II)-catalyzed meta- and para- selective arene diversification.5 Also, late-stage peptide
diversification6 and electrochemical C–H activations will be discussed.
Figure 1
[1] Ackermann, L.; Vicente, R.; Kapdi, A. Angew. Chem. Int. Ed. 2009, 48, 9792. [2] Ackermann, L. Chem. Rev. 2011, 111, 1315. [3] Selected example: Yang, F.; Koeller, J.; Ackermann, L. Angew. Chem. Int. Ed. 2016, 55, 4759. [4] Ackermann, L. Acc. Chem. Res. 2014, 47, 281. [5] Li, J.; Warratz, S.; Zell, D.; De Sarkar, S.; Ishikawa, E. E.; Ackermann, L. J. Am. Chem. Soc. 2015, 137, 13894. [6] Bauer, M.; Wang, W.; Lorion, M. M.; Dong, C.; Ackermann, L. Angew. Chem. Int. Ed. 2018, 57, 203 [7] a) Tian, C.; Massignan, L.; Meyer, T. H.; Ackermann, L. Angew. Chem. Int. Ed. 2018, 57, 2383; b) Sauermann, N.; Meyer, T. H.; Tian, C.; Ackermann, L. J. Am. Chem. Soc. 2017, 139, 18452.
LECTURES
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Synthesis and Applications of Novel Organogold Complexes M. Conception Gimenoa*
Lecture 4, September 1, 11:00 Departamento de Química Inorgánica. Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-
Universidad de Zaragoza, E-50009, Spain. [email protected]
Interest in the synthesis of new organogold complexes has revived in the last years because of the increasing
applications of gold complexes, particularly within the areas of homogenous catalysis, material chemistry or
medicine. Many novel organogold compounds have been synthesised in the search for new and more active
catalysts, for a better understanding of the catalytic mechanism, including the isolation of key catalytic
intermediates, or in the hunt of complexes with unique structure and properties. Several sort of ligands, which
provide high stability to the final compounds, such as alkynyl or N-heterocyclic carbenes have helped to the
development of this field. Moreover, other new types of ligands have been incorporated to the chemistry of this
metal.
Alkynyl or propargyl ligands are excellent building blocks that offer the possibility for the synthesis of
unusual gold complexes from a structural and bonding point of view, or in the construction of polymetallic
complexes with unique luminescent properties.1 The ease functionalisation of imidazolium salts with different
fragments allows tuning the properties of NHC gold complexes. Thus, whereas the use of bulky substituents
may confer great stability and rigidity for the use of the NHC gold complexes in catalysis,2 the presence of
fluorophore groups could led to luminescence properties with potential applications in the fabrication of
OLEDs,3 or the introduction of directing or water soluble groups could made the compounds of interest for
biological applications.4
[1] Long, N. J.; Williams, C. K. Angew Chem Int Ed. 2003, 42, 2586-2617. [2] Marion, N.; Nolan, S. P. Chem. Soc. Rev. 2008, 37, 1776-1782. [3] Visbal, R.; Gimeno, M. C. Chem. Soc. Rev. 2014, 43, 3551-3574. [4] Mora, M.; Gimeno, M. C.; Visbal, R. Chem. Soc. Rev. 2019, 48, 447-462.
LECTURES
17
Light-Emitting Organometallic Complexes: from Design Principles and Excited
States to Applications in OLEDs & Bio-Imaging
J. A. Gareth Williamsa*
Lecture 5, September 1, 14:30 a Department of Chemistry, Durham University, Durham, DH1 3LE, U.K.
The lecture will introduce the concepts used in understanding the luminescence properties of transition metal
complexes, including the classification of excited states according to the orbitals involved. Efficiencies of
emission (quantum yields) are determined by the relative values of radiative and non-radiative decay rate
constants. Excited states that are highly distorted relative to the ground state typically suffer from severe non-
radiative decay: the lack of emission from most 1st row transition metal complexes is generally due to the
population of low-energy d-d states which are highly distorted. Moving to the 2nd and 3rd row transition metals,
ligand field strengths increase, allowing emission to compete with non-radiative decay. Spin-orbit coupling
(SOC) also increases, and the triplet states then dominate much of the chemistry. SOC can promote
phosphorescence from triplet states, provided that the metal makes a significant contribution to pertinent
molecular orbitals.1 In many cases, this can be achieved by cyclometallation.
The principles introduced in the first half of the lecture will then be used in a case study of platinum(II)
complexes. The properties of a family of N^C^N-coordinated complexes will be described,2 including colour
tuning by manipulation of the ligand substituents or identity of the co-ligand, and the potential importance of
excimer formation. Examples of OLEDs fabricated using these compounds will be presented, including white-
and near-IR-emitting devices.3 Finally, we shall discuss how the long-lived phosphorescence of such complexes
offers unusual opportunities in bio-imaging, allowing interference from background fluorescence to be
suppressed.4
Figure 1 Left: N^C^N- and N^C-binding modes of dipyridyl benzene (dpyb) to metals; centre: colour tuning
of OLEDs incorporating Pt(dpyb)Cl as a phosphor; right: time-resolved bio-imaging with Pt(dpyb)Cl.
[1] Yersin, H.; Rausch, A. F.; Czerwieniec, T.; Hofbeck, T.; Fischer, T. Coord. Chem. Rev. 2011, 255, 2622. [2] Williams, J. A. G. Chem. Soc. Rev. 2009, 38, 1783. [3] Kalinowski, J.; Fattori, V.; Cocchi, M.; Williams, J. A. G. Coord. Chem. Rev., 2011, 255, 2401. [4] Baggaley, E.; Botchway, S. W.; Haycock, J. W.; Morris, H.; Sazanovich, I. V.; Williams, J. A. G.; Weinstein, J. A. Chem. Sci. 2014, 5, 879.
LECTURES
NN
N
NM
M
1
2
3
45
6
12
3
45
6
N^C^N binding mode N^C binding modefavoured by Pt(II)
also Ru(II) and Os(II)favoured by Pd(II), Ir(III), Rh(III)
18
Organometallic Catalysis for New Molecular Architectures
Simon Woodward,a* Jens Pflaum,b Martins Rutkis, Vladimir Dimitrovc
Lecture 6, September 2, 09:00 a GSK Carbon Neutral Laboratories for Sustainable Chemistry, Jubilee Campus, University of Nottingham, Nottingham
NG7 2TU, United Kingdom. b Experimental Physics VI, University of Würzburg, Am Hubland, 97074Würzburg, Germany. c Institute of Solid State Physics, University of Latvia, Rīga, LV-1063, Latvia. b Institute of Organic Chemistry
with Centre of Phytochemistry, Sofia 1113, Bulgaria [email protected]
The tetracene derivatives of Figure 1 are potentially useful for the development of a wide range of
organoelectronic devices including field effect transistors, photovoltaics, and especially thermoelectrics.1-5
Unfortunately, despite their simple constitution, there is no natural source of the tetracene core on Earth and
their total synthesis is always required. The latter is hindered by the low solubility and partial air sensitivity of
such species. For widespread application of waste heat recovery and new cool technologies high efficiency
syntheses of tetracenes is required. This tutorial lecture will present such routes together with our first steps
towards device technologies, in a way accessible to synthetic chemists.
Figure 1
[1] Capturing Waste Heat Energy with Charge-Transfer Organic Thermoelectrics, V. Dimitrov, S. Woodward, Synthesis 2018, DOI: 10.1055/s-0037-1610208 (link). [2] Synthesis and Thermoelectric Properties of 2- and 2,8-Substituted Tetrathiotetracenes, M. R. Garrett, M. J. Durán-Peña, W. Lewis, K. Pudzs, J. Uzulis, I. Mihailovs, B. Tyril, J. Shine, E. F. Smith, M. Rutkis, S. Woodward, J. Mater. Chem. C 2018, 6, 3403-3409 (link). [3] Straightforward Synthesis of 2- and 2,8-Substituted Tetracenes, S. Woodward, M. Ackermann, S. Ahirwar, L. Burroughs, M. R. Garrett, J. Ritchie, J. Shine, B. Tyril, K. Simpson, P. Woodward, Chem. Eur. J. 2017, 23, 7819-7824 (link). [4] Low-Cost and Sustainable Organic Thermoelectrics Based on Low-Dimensional Molecular Metals, F. Huewe, A. Steeger, K. Kostova, L. Burroughs, I. Bauer, P.Strohriegl, V. Dimitrov, S. Woodward, Jens Pflaum, Adv. Mater. 2017, 29, 1605682 (link). [5] Thin film organic thermoelectric generator based on tetrathiotetracene, K. Pudzs, A. Vembris, M. Rutkis, S. Woodward, Adv. Electron. Mater. 2017, 3, 1600429 (link).
LECTURES
19
Exploiting Organometallic Chemistry for Biomedical Applications
Angela Casinia* Lecture 7, September 2, 11:00
a Chair of Medicinal and Bioinorganic Chemistry, Department of Chemistry, Technical University of Munich, Lichtenbergstr. 4, 85747 Garching bei München, Germany.
The peculiar chemical properties of metal-based drugs impart innovative pharmacological profiles to this
class of therapeutic and diagnostic agents, most likely in relation to novel molecular mechanisms still poorly
understood. However, inorganic drugs have been scarcely considered for medicinal applications with respect
to classical organic compounds due to the prejudice of the relevant toxic effects observed in certain cases. Thus,
the development of improved metallodrugs requires clearer understanding and control of their physiological
processing (speciation) and molecular basis of actions. In this context, different families of organometallic
complexes, endowed with stability and robustness of functionalization, including N-heterocyclic carbenes and
alkynyl complexes, as well as cyclometalated compounds have shown promising therapeutic (anticancer)
properties in vitro and in vivo.1
One of the challenges of modern medicinal inorganic chemistry is translating the potential of metal catalysts
to living systems to achieve controlled non-natural transformations for therapy and imaging. This field poses
numerous issues associated to the metal compounds biocompatibility, stability and reactivity in complex
aqueous environment. Moreover, it should be noted that although referring to “metal catalysis”, turnover has
not yet been fully demonstrated in most of the examples with living systems. Recently, gold complexes, both
coordination and organometallics, have emerged as extremely promising for bioorthogonal transformations
being endowed with excellent reactivity and selectivity, compatibility with aqueous reaction medium, fast
kinetic of ligand exchange reactions and mild reaction conditions.2 Thus, a number of examples of gold-
templated reactions in a biologically relevant context will be presented and discussed in relation to their
potential applications in medicinal chemistry and chemical biology (Figure 1).
Figure 1
[1] Metallo-Drugs: Development and Action of Anticancer Agents. Metal Ions in Life Sciences. Edited by Sigel, A.; Sigel, H.; Freisinger, E.; Sigel, R.K.O. Walter de Gruyter, GmbH; 2018, 1992. [2] Wenzel M.N.; Bonsignore, R.; Thomas, S.R.; Bourissou, D.; Barone. G.; Casini, A. Chem. Eur J. 2019, doi:10.1002/chem.201901535.
NH
HN
O
SH
NH
HN
O
SR
NAu
R
NAu
X X
PBS (pH 7.4) r.t. NH
HN
O
S
R
N
REDUCTIVE ELIMINATION
R = CO, NH, CH2
LECTURES
20
Selective Synthesis and Catalysis via Diazo Decomposition Reactions
and Reactive Metal Carbenes
Jérôme Lacoura* Lecture 8, September 2, 14:30
a Department of Organic Chemistry, University of Geneva, Quai E. Ansermet 30, 1211 Geneva, Switzerland. [email protected]
Studies on metal-catalyzed reactions and processes will be presented – and those involving dirhodium,1
CpRu2 and copper3 catalyzed decompositions of α-diazocarbonyls and N-sulfonyl triazoles in particular. An
attention will be given to routes affording ylide intermediates and then functionally-rich heterocyclic
derivatives. A large variety of stereoselective and enantiospecific transformations are available through these
metal carbene reactions. Mechanistic investigations will be particularly detailed during the lecture. Applications
to a variety of topics from enantioselective synthesis to chiroptical spectroscopy will be mentioned.4
[1] Homberg, A.; Poggiali, D.; Vishe, M.; Besnard, C.; Guénée, L.; Lacour, J., Org. Lett. 2019, 687-691. Bosmani, A.; Guarnieri-Ibáñez, A.; Goudedranche, S.; Besnard, C.; Lacour, J., Angew. Chem. Int. Ed. 2018, 57, 7151-7155. Guarnieri-Ibáñez, A.; Medina, F.; Besnard, C.; Kidd, S. L.; Spring, D. R.; Lacour, J., Chem. Sci. 2017, 8, 5713–5720. Poggiali, D.; Homberg, A.; Lathion, T.; Piguet, C.; Lacour, J., ACS Catal. 2016, 6, 4877-4881. Medina, F.; Besnard, C.; Lacour, J., Org. Lett. 2014, 16, 3232-3235. Vishe, M.; Hrdina, R.; Guénée, L.; Besnard, C.; Lacour, J., Adv. Synth. Catal. 2013, 355, 3161 – 3169. Sharma, A.; Guénée, L.; Naubron, J.-V.; Lacour, J., Angew. Chem. Int. Ed. 2011, 50, 3677-3680. Rix, D.; Ballesteros-Garrido, R.; Zeghida, W.; Besnard, C.; Lacour, J., Angew. Chem. Int. Ed. 2011, 50, 7308-7311. Zeghida, W.; Besnard, C.; Lacour, J., Angew. Chem. Int. Ed. 2010, 49, 7253–7256. [2] Egger, L.; Guénée, L.; Bürgi, T.; Lacour, J., Adv. Synth. Catal. 2017, 359, 2918-2923. Tortoreto, C.; Achard, T.; Egger, L.; Guénée, L.; Lacour, J., Org. Lett. 2016, 18, 240–243. Achard, T.; Tortoreto, C.; Poblador-Bahamonde, A. I.; Guénée, L.; Bürgi, T.; Lacour, J., Angew. Chem. Int. Ed. 2014, 53, 6140–6144. Tortoreto, C.; Achard, T.; Zeghida, W.; Austeri, M.; Guénée, L.; Lacour, J., Angew. Chem. Int. Ed. 2012, 51, 5847-5851. [3] Goudedranche, S.; Besnard, C.; Egger, L.; Lacour, J., Angew. Chem. Int. Ed. 2016, 55, 13775-13779. Harthong, S.; Brun, E.; Grass, S.; Besnard, C.; Bürgi, T.; Lacour, J., Synthesis 2016, 48, 3254-3262. [4] Zinna, F.; Voci, S.; Arrico, L.; Brun, E.; Homberg, A.; Bouffier, L.; Funaioli, T.; Lacour, J.; Sojic, N.; Di Bari, L., Angew. Chem. Int. Ed. 2019, 58, 6952 –6956. Homberg, A.; Hrdina, R.; Vishe, M.; Guénée, L.; Lacour, J., Org. Biomol. Chem. 2019, 17, 6905-6910. Ray, S. K.; Homberg, A.; Vishe, M.; Besnard, C.; Lacour, J., Chem. Eur. J. 2018, 24, 2944-2951. Homberg, A.; Brun, E.; Zinna, F.; Pascal, S.; Górecki, M.; Monnier, L.; Besnard, C.; Pescitelli, G.; Di Bari, L.; Lacour, J., Chem. Sci. 2018, 9, 7043-7052. Jarolimova, Z.; Vishe, M.; Lacour, J.; Bakker, E., Chem. Sci. 2016, 7, 525-533. Vishe, M.; Hrdina, R.; Poblador-Bahamonde, A. I.; Besnard, C.; Guénée, L.; Bürgi, T.; Lacour, J., Chem. Sci. 2015, 6, 4923-4928.
LECTURES
21
Palladium(0)-Catalyzed C(sp3)-H Activation: from Method Development to
Natural Product Synthesis
Olivier Baudoin a* Lecture 9, September 2, 16:00
a University of Basel, Department of Chemistry, St. Johanns-Ring 19, CH-4056 Basel, Switzerland. [email protected]
Research efforts from our group in the past decade have focused on the functionalization of non-activated
C(sp3)-H bonds using catalysis by palladium(0) complexes.1
Figure 1
This lecture will present some of the most recent aspects of this chemistry, including enantioselective
reactions using different types of chiral catalysts,2 and applications in heterocycle3 and natural product
synthesis.4
[1] O. Baudoin, Acc. Chem. Res. 2017, 50, 1114. [2] a) P. M. Holstein, M. Vogler, P. Larini, G. Pilet, E. Clot, O. Baudoin, ACS Catal. 2015, 5, 4300; b) L. Yang, R. Melot, M. Neuburger, O. Baudoin, Chem. Sci. 2017, 8, 1344; c) L. Yang, O. Baudoin, Angew. Chem. Int. Ed. 2018, 57, 1394. [3] a) P. M. Holstein, D. Dailler, J. Vantourout, J. Shaya, A. Millet, O. Baudoin, Angew. Chem. Int. Ed. 2016, 55, 2805; b) D. Dailler, R. Rocaboy, O. Baudoin, Angew. Chem. Int. Ed. 2017, 56, 7218; c) R. Rocaboy, D. Dailler, F. Zellweger, M. Neuburger, C. Salomé, E. Clot, O. Baudoin, Angew. Chem. Int. Ed. 2018, 57, 12131. [4] a) D. Dailler, G. Danoun, O. Baudoin, Angew. Chem. Int. Ed. 2015, 54, 4919; b) R. Rocaboy, D. Dailler, O. Baudoin, Org. Lett. 2018, 20, 772; c) R. Melot, M. V. Craveiro, T. Bürgi, O. Baudoin, Org. Lett. 2019, 21, 812.
Pd0/L cat. base
X H
LECTURES
22
Decarboxylative Coupling Reactions:
a Modern Strategy for C–C and C–Heteratom Bond Formation
Lukas Gooßena*
Lecture 10, September 3, 08:30 a Ruhr-Universität Bochum, Lehrstuhl für Organische Chemie I, ZEMOS 2/27, Universitätsstraße 150, 44801 Bochum.
Decarboxylative coupling reactions, i.e. reactions in which C–C bonds to carboxylate groups are cleaved
with formation of new carbon-carbon bonds, have recently evolved from a laboratory curiosity into a powerful
synthetic strategy. Their key benefit is that they draw on easily available carboxylic acids rather than expensive
organometallic reagents as sources of carbon nucleophiles. Decarboxylative couplings have been utilized e.g.
in syntheses of biaryls, vinyl arenes, aryl ketones and aryl ethers. The decarboxylative Chan-Evans-Lam
alkoxylation of benzoic acids then demonstrated that this reaction concept is applicable also to C–heteroatom
bond-forming reactions.
In recent variations of this reaction type, the carboxylate groups are first utilized as directing groups for
ortho-C–H functionalizations, and then either cleaved tracelessly or used as leaving groups in subsequent ipso-
substitution reactions. In such transformations, the arene substitution pattern of the benzoate substrates is
altered in a defined way, so that they ideally complement the preceding protocols.
In this lecture, the concept of decarboxylative couplings is explained starting from pioneering work of
Nielsson, Cohen, and Tsuji, covering state-of-the-art arylation and vinylation reactions, and giving an outlook
on contemporary light-mediated decarboxylative alkylations.
Further reading
[1] N. Rodríguez, L. Gooßen, Chem. Soc. Rev., 2011, 40, 5030-5048: Decarboxylative coupling reactions: a modern strategy for C–C bond formation (Review). [2] M. Pichette Drapeau, L. J. Gooßen, Chem. Eur. J. 2016, 22, 18654: Carboxylic acids as directing groups for C−H bond functionalization (Minireview).
R2
R1
ORR1
OR
HR1
RR1
COOHR1
R1
RXR2
OHX = Hal, OTf, OTs, OMs
or
[Ox]
[Ox]
M(OR)x
- CO2Pd / Cu / Ag catalysts
LECTURES
23
Contribution of Electrochemistry to Organometallic Catalysis
Anny Jutanda*
Lecture 11, September 3, 10:00 a Ecole Normale Superieure, Chemistry Department 24 Rue Lhomond, 75231 Paris Cedex 5, France.
In coordination Transition metal catalyzed reactions proceed via catalytic cycles which are a succession of
chemical steps involving organometallic species whose metal exhibits different oxidation states. Most
organometallic complexes may be oxidized or reduced. Consequently, they can be detected, generated and
characterized by electrochemical techniques (cyclic voltammetry, chronoamperometry, etc…). Moreover, their
reactivity can be followed by the same techniques, taking advantages that currents are proportional to the
concentrations of electroactive species at any times. It is thus possible to investigate the rate and mechanism of
the chemical steps of a catalytic cycle, to determine factors that control the efficiency of catalytic reactions.
The mechanism of palladium-catalyzed cross-coupling reactions will be presented.
Further reading
[1] C. Amatore, A. Jutand, Acc. Chem. Res. 2000, 33, 314. [2] A. Jutand, Eur. J. Inorg. Chem. 2003, 2017. [3] A. Jutand, Chem. Rev. 2008, 108, 2300. [4] C. Amatore, G. Le Duc A. Jutand, Chem. Eur. J. 2013, 19, 10082.
LECTURES
24
Synthesis and Applications of Cationic Phosphines
Manuel Alcarazoa*
Lecture 12, September 3, 11:45 a Institute for Organic and Biomolecular Chemistry. Faculty of Chemistry, University of Göttingen, Tammannstr 2,
Göttingen 37077, Germany. [email protected]
In coordination chemistry, typical ancillary ligands are anionic or neutral species. Cationic ones are
exceptions and, when used, the positively charged groups are normally attached to the periphery and not close
to the donating atom. However, a series of recent experimental, as well as theoretical results suggested that the
utility in catalysis of cationic phosphines with no spacer between the phosphorus atom and the positively
charged groups, for example cyclopropenium, pyridinium or imidazolium substituted phosphines, have been
largely overlooked. In fact, our group has demonstrated that because of their specific architecture, these cationic
ligands depict excellent π-acceptor character that can exceed that of phosphites or polyfluorinated phosphines.
This property has been used to increase the Lewis acidity of the metals they coordinate.1 The application of
these ligands in Au-, Pt-, and Rh-catalysis, as well as their limitations, will be discussed.
Figure 1: Frontier orbitals for cationic phosphines at the B3LYP-D3/def2-TZVP level of theory
[1] (a) Tinnermann, H.; Nicholls, L.D.M.; Johannsen, T.; Wille, C.; Golz, C.; Goddard, R.; Alcarazo. M., ACS Catal. 2018, 8, 10457-10463; (b) González-Fernández, E.; Nicholls, L. D. M.; Schaaf, L. D.; Farès, C.; Lehmann, C. W.; Alcarazo, M., J. Am. Chem. Soc. 2017, 139, 1428-1431; (c) Gu, L.; Wolf, L. M.; Zieliński, A.; Thiel, W.; Alcarazo, M., J. Am. Chem. Soc. 2017, 139, 4948-4953; (d) Alcarazo, M., Acc. Chem. Res. 2016, 49, 1797-1805; (e) Dube, J. W.; Zheng, Y.; Thiel, W.; Alcarazo, M.; J. Am. Chem. Soc. 2016, 138, 6869-6877.; (f) Alcarazo, M. Chem. Eur. J. 2014, 20, 7868-7877.
LECTURES
25
Supramolecular Interactions in Polyaromatic N-Heterocyclic Carbenes. Host-
Guest Chemistry Properties and Catalytic Implications
Eduardo Perisa* Lecture 13, September 4, 09:00
a Institute of Advanced Materials (INAM). Universitat Jaume I. 12006 Castellón, Spain. [email protected]
In the course of our recent research, we demonstrated how homogeneous catalysts with polyaromatic
functionalities possess properties that clearly differ from those shown by analogues lacking these polyaromatic
systems. The differences arise from the ability of the polyaromatic groups to afford non-covalent interactions
with aromatic molecules, which can either be substrates in a homogeneous catalysed reaction, or the same
catalysts to afford self-assembled systems.1 This presentation summarizes all our efforts toward understanding
the fundamental effects of p-stacking interactions in homogenous catalysis, particularly in those cases where
catalysts bearing polyaromatic functionalities are used. The study reveals several important implications
regarding the influence of ligand-ligand interactions, ligand-additive interactions, and ligand-substrate
interactions, in the performance of the catalysts used.2 The nature and the magnitude of these supramolecular
interactions were unveiled by using host-guest chemistry methods applied to organometallic catalysis.3
The development of a wide variety of N-heterocyclic carbene ligands with extended polyaromatic
functionalizations also allowed us to prepare a large variety of metallo-supramolecular complexes, including
metallotweezers,4 metallo-rectangles,5 metallo-folders6 and metallo-cages.7 Depending on their structural
features, these species were used for the recognition of a variety of organic substrates, such as electron-
deficient aromatic substrates, polycyclic aromatic hydrocarbons and heavy metal cations.
[1] M. Raynal, P. Ballester, A. Vidal-Ferran, P. W. N. M. van Leeuwen, Chem. Soc. Rev. 2014, 43, 1660-1733. [2] E. Peris, Chem. Commun. 2016, 52, 5777-5787. [3] a) S. Ibañez, M. Poyatos, E. Peris, Organometallics 2017, 36, 1447-1451; b) S. Ruiz-Botella, E. Peris, Chem. Eur. J. 2015, 21, 15263-15271; c) S. Gonell, M. Poyatos, E. Peris, Angew. Chem. Int. Ed. 2013, 52, 7009-7013. [4] a) S. Ibanez, M. Poyatos, E. Peris, Angew. Chem. Int. Ed. 2018, 57, 16816-16820; b) S. Ibanez, E. Peris, Chem. Eur. J. 2018, 24, 8424-8431; c) S. Ibañez, M. Poyatos, E. Peris, Angew. Chem. Int. Ed. 2017, 56, 9786-9790. [5] a) V. Martínez-Agramunt, T. Eder, H. Darmandeh, G. Guisado-Barrios, E. Peris, Angew. Chem. Int. Ed. 2019, 58, 5682-5686; b) V. Martinez-Agramunt, S. Ruiz-Botella, E. Peris, Chem. Eur. J. 2017, 23, 6675-6681. [6] D. Nuevo, S. Gonell, M. Poyatos, E. Peris, Chem. Eur. J. 2017, 23, 7272-7277. [7] a) V. Martinez-Agramunt, D. Gusev, E. Peris, Chem. Eur. J. 2018, 24, 14802-14807; b) S. Ibañez, E. Peris, Angew. Chem. Int. Ed. 2019, 58, 6693-6697.
LECTURES
26
Metal Catalysed Hydrogen Transfer and Hydrogen Addition Reactions for the
Synthesis of Active Pharmaceutical Ingredients
Maurizio Taddei a*
Lecture 14, September 4, 10:45 aDipartimento di Biotecnologie, Chimica e Farmacia, Università degli Studi di Siena, Via A. Moro 2, 53100 Siena, Italy.
An Active Pharmaceutical Ingredient (API) is a substance used in a pharmaceutical product intended to
furnish pharmacological activity or to otherwise have direct effect in the diagnosis, cure, mitigation, treatment
or prevention of disease. After Pacific Asia, Western Europe is the second global producer and Italy is by far
the largest API producer in Europe. The vast majority of production are organic molecules obtained in
multigram (often kilogram) scale after several synthetic steps. As waste disposal and management have
impacted more and more on the final product price over the years, development of metal catalyzed processes
that minimize the waste production has become an important tool for API production. Metal catalyzed hydrogen
transfer and hydrogen addition reactions are very useful methods to control red-ox levels and to generate not
only C-H but also new C-C, C-N and C-O bonds. In this lecture, the application of hydrogenation, hydrogen
borrowing reactions, hydroformylation, hydrocarbonylation and metal catalyzed reductive amination reaction
to the synthesis of several APIs (some of them reported in Scheme 1) will be discussed, focusing on setting-up
procedures in the presence of functional groups often containing nitrogens. The key introduction of the metal
catalyzed hydrogen transfer reaction will be also discussed in streamlining the overall synthetic procedure.
Scheme 1
Further reading
[1] Taddei, M.; Giannotti, L.; Attolino, E.; Allegrini, P. EP2778165A1, 2014. [2] Taddei, M.; Cini, E.; Rasparini, M.; Taddei, M. WO2015056164A1, 2015. [3] a) Cini, E.; Banfi, L.; Barreca, G.; Carcone, L.; Malpezzi, L.; Manetti, F.; Marras, G.; Rasparini, M.; Riva, R.; Roseblade, S.; Russo, A.; Taddei, M.; Vitale, R.; Zanotti-Gerosa, A. Org. Process Res. Dev. 2016, 20, 270. b) Arena, G.; G.; Barreca, G.; Carcone, L.; Cini, E.; Marras, G.; Nedden, H. G.; Rasparini, M.; Roseblade, S.; Russo, A.; Taddei, M.; Zanotti-Gerosa, A. Adv. Synth. Catal. 2013, 355, 1449. [4] Giannini, G.; Vesci, L.; Battistuzzi, G.; Vignola, D.; Milazzo, F. M.; Guglielmi; Mor, M.; Rivara, S.; Pala, D.; Taddei, M.; Pisano, C.; Cabri, W. J. Med. Chem. 2014, 57, 8358.
LECTURES
27
Glycoconjugated Carbene Pt(II) Complexes as Anticancer Agents Poster 1
Alfonso Annunziata,a,b* Roberto Esposito,a,b Maria Elena Cucciolito,a,b Valerio Pinto,a Angela Tuzi,a
Antonello Merlino,a Daria Maria Monti,a Francesco Ruffoa,b
aDipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia 21, I-80126, Napoli (NA), Italy.
bConsorzio Interuniversitario di Reattività Chimica e Catalisi, via Celso Ulpiani 27, I-70126 Bari, Italy. [email protected]
Platinum based complexes play a key role as anticancer agents in current medical therapy. Nevertheless,
remarkable side effects and low selectivity against tumor cells motivate the design of new potential agents with
increased performance and improved pharmacological action.1 It is well known that the carbohydrates
metabolism is deeply altered in cancer cells, in which the demand and consumption of glucose is highly
increased respect to heathy cells (Warburg Effect).2 This condition has inspired the design of glycoconjugate
platinum complexes to exploit the selective recognition of glycosyl fragment by tumor cells. In this context, we
have previously reported the synthesis of five-coordinate Pt(II) bearing sugar based ligand, which revealed to
be active and fairly selective towards a number of cell lines.3,4 The present work is based on the design of new
platinum(II)5 complexes, containing N-heterocyclic carbene bearing different sugar residues, of the general
type sketched in Figure 1. The synthesis and characterization of the complexes have been performed, along
with the evaluation of the biological activity and the interaction with biological targets (DNA and model
proteins).
/
Figure 1
[1] P. Zhang and P. J. Sadler, J. Organomet. Chem., 2017, 839, 5. [2]A. Pettenuzzo, R. Pigot and L. Ronconi, Metallodrugs, 2016,1, 36. [3]M. E. Cucciolito, A. D’Amora, G. De Feo, G. Ferraro, A. Giorgio, G. Petruk, D. M. Monti, A. Merlino and F. Ruffo, Inorg. Chem., 2018, 57, 3133. [4].M. E. Cucciolito, F. De Luca Bossa, R. Esposito, G. Ferraro, A. Iadonisi, G. Petruk, L. D’Elia, C. Romanetti, S. Traboni, A. Tuzi, D. M. Monti, A. Merlino and F. Ruffo, Inorg. Chem.Front., 2018, 5, 2921. [5] A. Annunziata, M.E. Cucciolito, R. Esposito, P. Imbimbo, G. Petruk, G. Ferrato, V. Pinto, A. Tuzi, D.M. Monti, A. Merlino and F. Ruffo, Dalton Trans., 2019, 48, 7794.
POSTERS
28
Hydrosoluble Coinage Metal N-Heterocyclic Carbene Complexes: Synthesis and
Anticancer Studies
Poster 2
Luca Bagnarelli,a* Carlo Santini,a Riccardo Vallesi,a Cristina Marzano,b Valentina Gandinb and Maura Pelleia
a School of Science and Technology, Chemistry Division, University of Camerino, Italy. b Department of Pharmaceutical
and Pharmacological Sciences, University of Padova, Italy. [email protected]
N-heterocyclic carbenes (NHCs) are an interesting class of ligands with donor properties similar to
phosphanes. Their chemical versatility not only implies a wide variety of structural diversity and coordination
modes, but also a capability to form stable complexes with a large number of transition metals with different
oxidation states. In particular, NHC complexes of coinage metals have recently showed to be good candidates
as an alternative to cisplatin, exhibiting encouraging results in the field of anticancer drugs research.1,2 In the
last years, we have developed several classes of coinage metal-NHC complexes obtained from the precursors
{[HB(HImR)3]Br2} (R = Bn, Mes and t-Bu), {H2C(HTzR)2} and {H2C(HImR)2} (R = (CH2)3SO3- or (CH2)2COO-
).1 Recently we have focused the research work on 11th group metal-NHCs complexes obtained from
hydrosoluble 1,3-symmetrically and 1,3-unsymmetrically substituted NHCs precursors based on imidazole and
benzimidazole scaffolds.3,4 More recently we have synthesized and investigated the cytotoxic activity of the
novel NHC ligand precursor [HTz(pNO2Bn)2]Br, and the corresponding metal complexes M[Tz(pNO2Bn)2]Br (M =
Cu(I), Ag(I) or Au(I)).5 In addition, novel water-soluble bis(NHCSO3)CuCl complexes (NHCSO3 = HImBn,PrSO3,
Na(4-Me)ImPrSO3 and NaBzimPrSO3), derived by the sulfonated N-heterocyclic carbene precursors HImBn,PrSO3
(3-(1-benzyl-1H-imidazol-3-ium-3-yl)propane-1-sulfonate), Na(4-Me)HImPrSO3 (sodium 3,3'-(4-methyl-1H-
imidazole-3-ium-1,3-diyl)dipropane-1-sulfonate) and NaHBzimPrSO3 (sodium 3,3'-(1H-benzo[d]imidazole-3-
ium-1,3-diyl)dipropane-1-sulfonate), have been synthesized.6 The in vitro antitumor effects of the complexes
and the corresponding free ligands were evaluated on a panel of various human tumour cell lines. Their
cytotoxic properties were also evaluated against non-transformed human cells and on a cellular model of
cisplatin-resistance.
[1] Marinelli M., Santini C. and Pellei M., Curr. Top. Med. Chem. 2016, 16, 2995. [2] Porchia M., Pellei M., Marinelli M., Tisato F., Del Bello F., Santini C., Eur. J. Med. Chem. 2018, 146, 709. [3] Gandin V., Pellei M., Marinelli M., Marzano C., Dolmella A., Giorgetti M. and Santini C., J. Inorg. Biochem. 2013, 129, 135. [4] Marinelli M., Pellei M., Cimarelli C., Dias H.V. R., Marzano C., Tisato F., Porchia M., Gandin V., Santini C., J. Organomet. Chem. 2016, 806, 45. [5] Pellei M., Gandin V., Marinelli M., Orsetti A., Del Bello F., Santini C., Marzano C., Dalton Trans. 2015, 44, 21041. [6] Pellei M., Gandin V., Marzano C., Marinelli M., Del Bello F., Santini C., Appl. Organomet. Chem. 2018, 32, e4185.
POSTERS
29
Unprecedented Use of a Deep Eutectic Solvent as Hydrogen Source for Ru(II)-
Catalyzed Transfer Hydrogenation of Carbonyl Compounds Under Mild
Conditions
Poster 3
Marzia Cavallo,a Cristina Prandi,a Rosario Figliolia,b Maurizio Ballico,b Walter Baratta,b Salvatore Baldinoa*
a Dipartimento di Chimica, Università di Torino, Via P. Giuria, 7, 10125 Torino, Italy. b DI4A, Università di Udine, Via
Cotonificio 108, 33100 Udine, Italy. [email protected]
Deep eutectic solvents (DESs) are systems formed from a eutectic mixture of Lewis or Brønsted acids and
bases which can contain a variety of anionic and/or cationic species.1 They have emerged in the last two
decades as a promising alternative to volatile organic compounds (VOCs).2 They have recently been used as
unconventional solvents in several and diverse synthetic transformations,2a among which transition metal
catalyzed hydrogenation,2b often showing novel reactivity, selectivity and efficiency compared to traditional
VOCs. In addition, DESs are not volatile, non-toxic, non-flammable, completely biodegradable and easy to
handle and synthesize. Given their peculiar properties, in our pursuit of simple and efficient catalysts for the
Ru(II)-mediated reduction of carbonyl compounds,3 we envisaged the possibility to employ DESs both as
reaction media and hydrogen sources, combining readily accessible Ru-precursors with different diphosphane
and diamine ligands.
Herein we report the unprecedented use of the eutectic mixture HCOOH/TBABr as hydrogen source in the
transfer hydrogenation of commercial-grade carbonyl substrates to their corresponding alcohols, catalyzed by
the in situ generated system [RuCl(μ-Cl)(η6-p-cymene)]2 / dppf under mild conditions.
[1] Smith, E. L.; Capper, G.; Abbot, A. P.; Ryder, K., S.; Chem. Rev. 2014, 114, 11060. [2] a) Alonso, D. A.; Baeza, A.; Chinchilla, R.; Guillena, G.; Pastor, I. M.; Ramón, D. J.; Eur. J. Org. Chem. 2016, 612. b) García-Álvarez, J.; Eur. J. Inorg. Chem. 2015, 5153. [3] Chelucci G.; Baldino S.; Baratta W.; Coord. Chem. Rev. 2015, 300, 29.
POSTERS
30
Straightforward Carbon Monoxide Release from Tertiary Carboxylic Acids
Mediated by High Valent Transition Metal Halides
Poster 4
Niccolò Bartalucci,a* Marco Bortoluzzi,b Stefano Zacchini,c Guido Pampaloni,a Fabio Marchettia
a Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Pisa (PI), Italy. b Dipartimento di Scienze
Molecolari e Nanosistemi, University of Venezia Ca’ Foscari, Venezia (VE), Italy. c Dipartimento di Chimica Industriale “Toso Montanari”, University of Bologna, Bologna (BO), Italy.
The decarbonylation of carboxylic acids/acyl chlorides is a useful organic transformation, which is normally
achieved by low valent transition metal compounds under harsh conditions,1 often involving an oxidative
addition step.2 The reactions of selected tertiary a-phenylcarboxylic acids with a series of high valent transition
metal halides led to the formation of tertiary carbocations following unusual extrusion of carbon monoxide at
ambient temperature. A plausible mechanistic pathway is proposed for the WCl6/(CPh3)COOH model reaction,
based on DFT calculations. After the preliminary chlorination of the organic substrate, the trityl carbocation is
finally afforded via an elusive oxocarbonium intermediate.3 Unstable tertiary carbocations are
straightforwardly converted into hydrocarbons through intra- and inter-molecular rearrangements.4
Figure 1
[1] a) A. John, M. O. Miranda, K. Ding, B. Dereli, M. A. Ortuno, A. M. Lapointe, G. W. Coates, C. J. Cramer, W. B. Tolman, Organometallics 2016, 35, 2391; b) G. Kraus, S. Riley, Synthesis 2012, 44, 3003; c) S. Maetani, T. Fukuyama, N. Suzuki, D. Ishihara, I. Ryu, Organometallics 2011, 30, 1389. [2] a) N. Rodríguez, L. J. Goossen, Chem. Soc. Rev. 2011, 40, 5030; b) P. Hermange, A. T. Lindhardt, R. H. Taaning, K. Bjerglund, D. Lupp, T. Skrydstrup, J. Am. Chem. Soc. 2011, 133, 6061; c) Y. Obora, Y. Tsuji, T. Kawamura, J. Am. Chem. Soc. 1995, 117, 9814. [3] a) G. A. Olah, S. J. Kuhn, W. S. Tolgyesi, E. B. Baker, J. Am. Chem. Soc. 1962, 84, 2733; b) G. A. Olah, M. Alemayehu, A. H. Wu, O. Farooq, G. K. Surya Prakash, J. Am. Chem. Soc. 1992, 114, 8042. [4] a) N. Bartalucci, M. Bortoluzzi, S. Zacchini, G. Pampaloni, F. Marchetti, Dalton Trans. 2019, 48, 1574; b) N. Bartalucci, F. Marchetti, S. Zacchini, G. Pampaloni, Dalton Trans. 2019, 48, 5725.
POSTERS
31
Site-Selective Hydrocarboxylation of Alkenes and Alkynes Via CO2 Activation
Catalyzed by Electrogenerated SmII Complex
Poster 5
Sokna Bazzi,a* Mohamed Mellaha
a Molecular catalysis laboratory, ICMMO (UMR 8182), Paris Sud University 91405 Orsay, France
Nowadays, Carbon dioxide is one of the most discussed topics after the IPCC’S report on the impact of global
warming related to increasing levels of this greenhouse gas (GHG) in the atmosphere.1 On the good side, its
unbeatable characteristics (cheap, available and inherently renewable gas) make the CO2 a very attractive
option to be considered and the best candidate to be used in organic chemistry, especially for C-C bond
formation reactions.2 However, the thermodynamic stability and the kinetic intertie remain an immense
obstacle in the way of its reduction. Particularly, the hydrocarboxylation reactions of unsaturated substrates
(mainly alkenes and alkynes) via CO2 activation to produce carboxylic acids are quite rare, notably those
leading to the anti-Markovnikov products, challenging for the metal catalysis.3
Herein, we report a simple, mild and efficient new method to overcome these barriers. By using a catalytic
amount of samarium dichloride (SmCl2), generated in situ by electrochemistry, we were able to reduce and
activate efficiently the CO2 delivering the radical anion CO2.-. This radical initiates then a selective anti
Markovnikov mechanism with the unsaturated starting material in the presence of tert-butanol as a proton
donor. Relaying on this new reactivity, we now have an excellent strategy to convert abundant feedstocks into
valuable carboxylic acids with no need for an expensive ligand or substoichiometric reductant.
[1] https://www.carbonbrief.org/in-depth-qa-ipccs-special-report-on-climate-change-at-one-point-five-c [2] Tortajada, A.; Juliá-Hernández, F.; Börjesson, M.; Moragas T.; Martin, R.; ACIE 2018, 57, 15948. [3] Meng, Q.-Y.; Wang, S.; Huff, G.S.; Konig, B.; JACS 2018, 140, 3198.
POSTERS
CO2 SmCl3
Alkenes or
Alkynes t-BuOH TMSCl
Saturated & unsaturated
R-COOH
e- e- e- e- e- e-
CO2
.-
CO2
.- CO2 CO2 CO
2
.-
CO2 CO2
.-
32
Synthesis and Characterization of Fe-M (M = Cu, Ag, Au) Heterobimetallic
Carbonyl Clusters Containing N-Heterocyclic Carbene Ligands
Poster 6
Beatrice Berti,a* Marco Bortoluzzi,b Cristiana Cesari,a Cristina Femoni,a Maria Carmela Iapalucci,a Rita Mazzoni,a Federico Vacca,a Stefano Zacchinia
a Dipartimento di Chimica Industriale "Toso Montanari", University of Bologna, Viale Risorgimento 4, I-40136
Bologna, Italy. b Dipartimento di Scienze Molecolari e Nanosistemi, Ca’ Foscari University of Venice, Via Torino 155, 30175 Mestre (Ve), Italy. [email protected]
The introduction of NHC ligands in metal carbonyl clusters may be useful in order to modulate their chemical
and physical properties, as well as to extend their applications in catalysis and organic synthesis.1 Moreover,
the employment of bulkier ligands in molecular clusters may help increasing their nuclearities with the final
purpose to prepare larger molecular nanoclusters. Herein we report the reactions of Na2[Fe(CO)4]·2thf with
M(NHC)Cl which afford [Fe(CO)4(MNHC)]-, Fe(CO)4(MNHC)2 and Fe(CO)4(MNHC)(M’NHC’). Their
thermal decomposition results in higher nuclearity species (Figure).2,3,4
Figure. From the left: molecular structures of [Fe(CO)4(AuIMes)]-, Fe(CO)4(CuIPr)2 and [Au16S{Fe(CO)4}4(IPr)4]n+.
[1] Hermann, W.A. Angew. Chem. Int. 2002, 41, 1290. [2] Bortoluzzi, M.; Cesari, C.; Ciabatti, I.; Femoni, C.; Hayatifar, M.; Iapalucci, M. C.; Mazzoni, R.; Zacchini, S. J. Clust. Sci. 2017, 28, 703-723. [3] Berti, B.; Bortoluzzi, M.; Cesari, C.; Femoni, C.; Iapalucci, M. C.; Mazzoni, R.; Vacca, F.; Zacchini, S. Eur. J. Inorg. Chem. 2019, 3084–3093. [4] Berti, B.; Bortoluzzi, M.; Cesari, C.; Femoni, C.; Iapalucci, M. C.; Mazzoni, R.; Vacca, F.; Zacchini, S. Inorg. Chem. 2019, 58, 2911−2915.
POSTERS
33
Nitrous Oxide as a Clean Oxidant: from Alcohols to Carboxylates
Poster 7
Jonas Bösken,a* Rafael E. Rodríguez-Lugo,a Hansjörg Grützmachera
a Department of Chemistry and Applied Biosciences, Federal Institute of Technology (ETH) Zurich, 8093 Zurich, Switzerland.
[email protected] Nitrous oxide (N2O) is an interesting reagent for oxidation chemistry because it can serve as a clean source
of an [O] atom with N2(g) as the only by-product.[1] However, its use is limited due to its kinetic inertness[2] and
typically a catalyst is required. Several heterogeneous catalysts have been successfully employed for oxidation
reactions with nitrous oxide,[1,3] but only few examples have been described with homogeneous catalysts.
Grützmacher et al. have developed Rh(I) and Co(0) amino-olefin complexes for the oxidation of alcohols[4] and
phosphines[5] respectively, employing N2O as oxidant. Here, the oxidation of light alcohols with nitrous oxide
catalyzed by a low-valent dinuclear ruthenium diazadiene complex [3-H2] is described.[6]
Scheme 1: Synthesis of catalyst 3-H2
We describe the oxidation of light alcohols with nitrous oxide catalyzed by a low-valent dinuclear ruthenium
diazadiene complex (1-H2).[6] The published synthesis of 1-H2 was improved (Scheme 1). To the best of our
knowledge, the present work is the first example of light alcohol oxidation employing N2O promoted by a
homogeneous catalyst. The dinuclear Ru complex [3-H2] is the most active homogeneous catalyst tested here.
Yields of up to 90 %, TONs of up to 480, and TOFs of up to 56 h-1 were achieved. Unusual MeOH
dehydrogenation towards formate was observed. The reaction proceeds under relatively mild conditions: 0.4
mol% catalyst, 80 °C, 4 h, ~ 2 bar N2O.
Scheme 2: Catalytic oxidation of light alcohols.
[1] Noskov, A.S. et al. Catal. Today 2005, 100, 115. [2] Eger, E.I. Nitrous Oxide N2O, Elsevier, New York, 1985 [3] Rodriguez-Lugo, R. E. et al. Inorg. Chim. Acta 2015, 431, 21 [4] Grützmacher, H. et al. Angew. Chem. Int. Ed. 2016, 55, 15323. [5] Grützmacher, H. et al. Angew. Chem. Int. Ed. 2016, 55, 1854. [6] Grützmacher, H. et al. Chem. Sci. 2019,10, 1117.
POSTERS
34
Synthesis of 2-Alkenylidene-3-Oxoindoles by Gold-Catalyzed Cascade Reaction
Poster 8
Elisa Brambilla,a* Valentina Pirovano,a Matteo Giannangeli,b Giorgio Abbiati,a Alessandro Caselli,b Elisabetta Rossia
a Dipartimento di Scienze Farmaceutiche, Sezione di Chimica Generale e Organica “A. Marchesini, Università degli Studi di Milano, Via Venezian 21, 20133 Milano (Italy). b Dipartimento di Chimica and ISTM-CNR, Università degli
Studi di Milano, Via Golgi 19, 20133 Milano (Italy). [email protected]
Homogeneous gold-catalyzed cascade reactions are important and useful process for the synthesis, inter
alias, of highly functionalized heterocycles and natural products.1 In this context, we recently investigated the
use of functionalized 4H-furo[3,2-b]indoles for the synthesis of more complex structures. Thus, 4H-furo[3,2-
b]indoles were explored for the synthesis of 2-spirocyclopentane-1,2-dihydro-3H-indolin-3-ones through the
addition of gold-activated allenes to the C2 furan moiety.2
Herein we present the evolution of this work involving the C2-C3 bond of 4H-furo[3,2-b]indoles in the
reaction with a gold(I)-carbene generated in situ from propargyl esters.3 In particular, reaction between 4H-
furo[3,2-b]indoles and propargyl esters, performed in presence of gold(I) catalysts, leads to the formation of 2-
alkenylidene-3-oxoindoles in a cascade process that includes a double ring opening step. A series of 2-
alkenylidene-3-oxoindoles were obtained in good to excellent yields. Optimization of the reaction conditions,
scope and proposed reaction mechanism will be illustrated in the poster, together with preliminary
photophysical studies.
Scheme 1
[1] a) Furstner, A. Angew. Chem., Int. Ed., 2018, 57, 4215; b) Quach, R.; Furkert, D. P.; Brimble, M. A. Org. Biomol. Chem., 2017, 15, 3098. [2] Pirovano, V.; Brambilla, E.; Rizzato, S.; Abbiati, G.; Bozzi, M.; Rossi, E. J. Org. Chem., 2019, 84, 5150. [3] Brambilla, E.; Pirovano, V.; Giannangeli, M.; Abbiati, G.; Caselli, A.; Rossi, E. Org. Chem. Front., 2019, DOI: 10.1039/C9QO00647H
POSTERS
35
Cytotoxic Performance of New Anionic Cyclometalated Pt(II) Complexes
Bearing Chelated O^O Ligands
Poster 9
Rossella Caligiuri,a* Andreea Ionescu,a,b Nicolas Godbert,a,b Loredana Ricciardi,b Massimo La Deda,a,b Mauro Ghedini,a,b Nicola Ferri,c Maria Giovanna Lupo,c Giorgio Facchetti,d Isabella
Rimoldi,d Iolinda Aielloa,b
a MAT-InLAB, LASCAMM CR-INSTM, Unità INSTM della Calabria, Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, Ponte Pietro Bucci Cubo 14C, 87036 Arcavacata di Rende (CS), Italy. b CNR
NANOTEC-Istituto di Nanotecnologia U.O.S. Cosenza, 87036 Arcavacata di Rende (CS), Italy. c Università degli Studi di Padova, Dipartimento di Scienze del Farmaco, Via Marzolo 5, 35131, Padua, Italy. d Università degli Studi di Milano,
Dipartimento di Scienze Farmaceutiche, Via Venezian 21, 20133 Milan, Italy. [email protected]
One of the most aggressive tumors with limited treatment options is the triple-negative breast cancer
(TNBC), that evinces a negative response to drugs due to the lack in the main three receptors, common targets
for the therapy against breast cancer. In this study, in vitro
biological activity on the MDA-MB-231, a TNBC cell line, of two
different series of anionic Pt(II) organometallic complexes were
studied. These are anionic compounds with general formula
NBu4[(C^N)Pt(O^O)] where (C^N) are the cyclometalated form
of 2-phenylpyridine (H(PhPy)), 2-thyenylpyridine (H(Thpy)) and
2-benzo[h]quinoline (H(Bzq)) that feature two different (O^O)
chelated ligands: the tetrabromocatechol (BrCat)2- (1-3) or
alizarine (Aliz)2- (4-6). Complexes 1-6 (Figure 1) displayed a
significant cytotoxic effect on the studied cell line (1.9-52.8 μM
IC50 range). For (BrCat)2- containing complexes, the biological
activity was independent on the nature of the coordinated (C^N)
ligand. In the case of 4-6, instead, the cytotoxicity (significantly
low for 4) was induced concomitantly by the presence of either
the PhPy and the (Aliz)2- ligands. Since complexes 1-6 are
emissive in solution, the potential use of the best performing
complex 4 as theragnostic agent was confirmed by fluorescence
confocal microscopy.
POSTERS
Figure 1: Chemical structures of cyclometalated anionic Pt(II) complexes 1-6.
36
Synthesis of Au and Cu β-Diiminate Complexes with Potential Catalytic Activity
in C-C/C-N Coupling Reactions
Poster 10
Andrea Cataffo,a* Peter H.M. Budzelaar
a Università degli Studi di Napoli Federico II, Via Cinthia, 80126 Fuorigrotta, Napoli NA, Italy,
β-Diiminate (BDI) anionic ligands are the nitrogen analogues of the well known β-diketonates. Variations
bearing 2,6-disubstituted aryl groups at N are good at stabilizing metals in low-coordinate environments,
leading to high, interesting and tunable reactivity. It is, in fact, relatively easy to change the substituents on the
aryls and at the backbone.1 The aim of this project is to isolate Au and Cu complexes of the type shown below
(A and B). Four different ligands and their lithium salts have been synthesized and characterized: this should
allow tuning of both steric (1 vs 2) and electronic (a vs b) properties of the complexes.
A B
Gold(III) bound to two methyl groups forms with the MeBDI ligand a complex (A-1a) which has been
reported to decompose after 3 h at room temperature.2 Replacing ligand 1a by 2a, 1b or 2b could avoid or
slow down decomposition caused by reductive elimination and formation of Au(0). For Gold (I), ligand
fluorination has also been suggested to increase stability of the chelate structure.3
Copper(II) amides, shown to present copper(I) - aminyl radical character, can be stabilized by a β-
diiminate ligand in a trigonal coordination environment.4 Starting from copper halides and lithium salts of BDI
ligands it is possible to synthesize (RBDI)CuX compounds;5 substituting the halide with an anilide would then
give a product of the type B. Once synthesized, it will be interesting to test the applications of these complexes
in different reactions, including C-C, C-N couplings (already seen for similar Rh(II) compounds6) , and
possibly in catalysis.
[1] Zhu, D.; Budzelaar, P. H. M., Dalton Trans., 2013, 42 (32), 11343-54. [2] Venugopal A., Ghosh M.K., Jϋrgens H., Tornroos K.W., Swang O., Tilset M., Heyn R.H., Organometallics, 2010, 29, 2248–2253 [3] Savjani N., Schormann M., Bochmann M., Polyhedron, 2012, 38, 137-140. [4] Melzer M., Mossin S., Dai X., Bartell A., Kapoor P., Meyer K., Warren T., Angew. Chem. Int. Ed, 2010, 49, 904-907. [5] Holland, P. L.; Tolman, W. B. J. Am. Chem. Soc. 1999, 121, 7270- 7271 [6] Zhang N., Zhu D, Herbert D., van Leest N., de Bruin B., Budzelaar P.H.M, Inorg. Chim. Acta 482, 2018, 709–716.
POSTERS
1. R = Me 2. R = iPr a) Z = CH3 b) Z = CF3
37
Blue Emitting Boron Difluoride Complexes of
2-(Imidazo[1,5-a]Pyridin-3-yl)Phenols
Poster 11
Gioele Colombo,a* Stefano Brenna,a G. Attilio Ardizzoiaa
a University of Insubria, Department of Science and High Technology (DiSAT), Via Valleggio 9 – 22100 Como, Italy
Imidazo[1,5-a]pyridines are a very well known class of heterocyclic compounds whose photochemical
properties have been widely explored; their most interesting characteristics are large Stoke shifts, high quantum
yields and, depending on their functionalization, a wide range of emission wavelength. If substituted with a
phenolic moiety, they can also act as bidentate ligands, providing the possibility of N-O coordination. It has
been reported, e.g., coordination to zinc(II)1 or silver(I)2 centers leading to the formation of fluorescent species.
Moreover, there are numerous publications on preparation of Organic Light Emitting Diodes (OLEDs) based
on such species, both ligands and complexes.3
Herein we discuss the fluorescent behavior of a series of boron difluoride functionalized imidazo[1,5-
a]pyridine phenols (Figure 1): the introduction of the BF2 moiety leads to a dramatic change in the emitting
properties, providing a series of blue emitting species, with also the possibility to introduce several substituents
(R) on the phenolic ring.
Figure 1: Boron complexes of imidazo[1,5-a]pyridine phenols object of this study.
[1] a) G.A. Ardizzoia, S. Brenna, S. Durini, B. Therrien, M. Veronelli, Eur. J. Inorg. Chem. 2014, 4310-4319; b) G.A. Ardizzoia, S. Brenna, S. Durini, B. Therrien, Polyhedron 2015, 90, 214-220; c) G.A. Ardizzoia, G. Colombo, B. Therrien, S. Brenna, Eur. J. Inorg. Chem. 2019, 1825-1831. [2] S. Durini, G.A. Ardizzoia, B. Therrien, S. Brenna, New. J. Chem. 2017, 41, 3006-3014. [3] See for examples: a) Nakatsuka, M.; Shimamura, T. Jpn. Kokai Tokkyo JP 2001035664, 2001; Chem. Abstr. 2001, 134, 170632; b) Tominaga, T.; Kohama, T.; Takano, A. Jpn. Tokai Tokkyo JP 2001006877, 2001; Chem. Abstr. 2001, 134, 93136; c) Kitasawa, D.; Tominaga, T.; Takano, A. Jpn. Kokai Tokkyo JP 2001057292, 2001; Chem. Abstr. 2001, 134, 200276.
POSTERS
38
The Influence of Asymmetric N-Heterocyclic Carbenes on Synthesis, Structure
and Activity of Dialkylgallium Alkoxides in the Polymerization of Rac-Lactide
Poster 12
Anna Maria Dabrowska,a,b* Pawel Horeglada
a Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland. b Centre of New Technologies, University of Warsaw, S. Banacha 2c, 02-097 Warsaw, Poland.
Dialkylgallium alkoxide complexes with N-heterocyclic carbenes (R2GaOR(NHC)) are a new class
of main-group metal alkoxides with NHCs, and have been proven to be stereoselective catalysts
in the polymerization of rac-lactide. Me2GaOR(NHC) (NHC = SIMes, IMes) complexes, first described
by our group, turned out to be highly active and isoselective catalysts in the polymerization of rac-lactide, even
at −20°C, which makes them one of the few described highly isoselective catalysts active under mild
conditions[1,2]. Moreover, the reaction of simple dialkylgallium alkoxides, which are non-stereoselective
or heteroselective depending on polymerization conditions, with NHCs leads to the formation of isoselective
R2GaOR(NHC), being the first example of a simple stereoselectivity switch in the polymerization
of rac-lactide, thus enabling the synthesis of polylactide (PLA) of new microstructure and properties [2,3].
Interestingly, the influence of the NHC, as well as the structure of NHC, on the activity and, most
importantly, isoselectivity of Me2Ga(OR)NHC complexes has not been explained so far. Therefore, in my
research, I have used asymmetric N-heterocyclic carbenes (asymmNHC) to synthesize and characterize
Me2Ga(OR)asymmNHC complexes. Moreover, I have focused on the effect of their structure on their catalytic
properties and stereoselectivity.
I am going to present how asymmNHCs influence the structure of Me2Ga(OR)asymmNHC complexes, as well
as its effect on the activity and stereoselectivity of Me2Ga(OR)asymmNHC, in comparison to their symmetric
analogues.
My research is financed by National Science Centre, grant Preludium no. 2016/23/N/ST5/03338
[1] Horeglad, P. et al. Chem. Commun. 48, 1171–1173 (2012) [2] Horeglad P. et al. Organometallics 34, 3480–3496 (2015) [3] Horeglad P. et al. Appl. Organometal. Chem., 27(6), 328–336 (2014)
POSTERS
39
Regio- and Chemoselective Michael Addition of Lithium Zincate Species to
Nitroolefins with No Additional Solvents: Synthetic and Structural Aspects
Poster 13
Marzia Dell’Aera,a,b* Filippo Maria Perna,a Paola Vitale,a Angela Altomare,b Alessandro Palmieri,c
Eva Hevia,d and Vito Capriatia
a Dipartimento di Farmacia-Scienze del Farmaco, Università di Bari “A. Moro”, Consorzio C.I.N.M.P.I.S., Via E. Orabona 4, I-70125 Bari, Italy. b Istituto di Cristallografia (IC-CNR),Via Amendola 122/o, I-70125 Bari, Italy. c
Dipartimento di Scienze Chimiche, Università di Camerino, Via S.Agostino 1, I-62032 Camerino, Italy. d Departement für Chemie und Biochemie, Universität Bern, Hochschulstrasse 6, 3012 Bern, Switzerland.
The conjugate addition of organometallics to nitroalkenes provides a useful method for nitro-alkylation.
This type of addition is much pursued in organic synthesis as the nitro group can be easily transformed into
various functional groups including carbonyl derivatives by the Nef reaction, amines by reduction, nitriles and
imines by other transformations1. While the 1,4-conjugated addition of organozinc reagents (R2Zn and RZnX)
has been extensively studied2, applications of alkali-metal zincates in fundamental organic transformations are
still in their infancy3. These type of reagents show unique, synergistic chemical characteristics which cannot
be replicated by their monometallic (organolithium/organozinc) counterparts. Furthermore, the replacement of
the vinylic nitro group by an alkyl group remains a complication encountered when nitrostyrenes are reacted
with dialkylzinc compounds in the absence of a Lewis acid4. In this Communication, we compare the kinetic
reactivity of two different alkali-metal zincates, namely triorgano- and tetraorganozincates, in Deep Eutectic
Solvents5 and under neat conditions, towards variously substituted nitroalkenes. Under optimised reaction
conditions (0 °C and with no additional solvents), Michael additions promoted by aliphatic and aromatic lithium
organozincates take place with high regio- and chemoselectivity, thereby providing the expected nitroalkanes
in yields up to >98% without replacement of the vinylic nitro group by the alkyl group (Scheme 1). Isolation
of key intermediates and structural aspects will be discussed as well.
Scheme 1
[1] Ono, N.; The Nitro Group in Organic Synthesis, Wiley-VCH, 2002. [2]. Feringa, B. L.; Pineschi, M.; Arnold, L. A.; Imbos, R.; H. M., de Vries A. Angew. Chem. Int. Ed. Engl., 1997, 36, 2620. [3] Armstrong, D. R.; Dougan, C.; Graham, D. V.; Hevia, E.; Kennedy, A. R. Organometallics, 2008, 27, 6063. [4] Schaefer, H.; Seebach, D. Tetrahedron, 1995, 2305-2324. [5] García-Álvarez, J.; Hevia, E; Capriati, V. Chem. Eur. J., 2018, 24, 14854.
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Enantioselective Tetrahydroquinolines Synthesis by One Pot Intramolecular
Hydroamination/Reduction Reaction Catalysed by Gold Nanoparticles Poster 14
Antonella Dentoni Litta,a* Alfonso Grassia
a University of Salerno Department of Chemistry and Biology “Adolfo Zambelli”, via Giovanni Paolo II, 132 - 84084
Fisciano (SA) Italy. [email protected]
Gold nanoparticles (AuNPs) have been found as active, selective and recyclable heterogeneous catalyst in
a wide range of organic reactions.1 Hydroamination of alkynes is a 100% atom-economical efficient process
which allows the direct formation of new carbon-nitrogen bonds; this reaction needs to be efficiently catalysed
in order to overcome the high activation barrier due to the repulsion between the nitrogen lone pair and alkyne
π-orbitals. Homogeneous gold catalysts based on (Ph3P)Au(I)X (X= Me, Cl) were reported as effective in the
one pot hydroamination of alkynes/asymmetric transfer hydrogenation of 2-(2-propynyl) anilines into
tetrahydroquinolines, giving the desired products in high yields (87-99%) and good enantioselectivity (82-99%)
in 16h in the presence of chiral Brønsted acid and Hantzsch ester.2
We found that e.g. the intramolecular hydroamination of 1 (Figure 1) catalysed by AuNPs followed by
asymmetric transfer hydrogenation gives 2 in 3h with good yields, regioselectivity and high enantioselectivity.
The catalyst is recyclable and active in green solvents.
Figure 1
The performances of the homogeneous and heterogeneous gold catalysts have been compared and discussed.
[1] Corma, A.; Garcia, A. E. Chem. Soc. Rev. 2008, 37, 2096. [2] Han, Z. Y.; Xiao, H.; Chen, X. H.; Gong, L. Z. J Am. Chem. Soc. 2009, 131, 9182.
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Oxidative Cleavage of High-Oleic Vegetable Oils
Poster 15
Massimo Melchiorre,a,b* Vincenzo Benessere,b Maria Elena Cucciolito,a,b Chiara Melchiorre,a Francesco Ruffo,a,b Roberto Espositoa,b*
a Università degli Studi di Napoli Federico II. b ISusChem S. R. L., Piazza Carità 32, 80134 Napoli, Italy.
[email protected], [email protected]
Within the new raw renewable sources, vegetable oils are an attractive chemical platform1,2 because they
possess versatile groups, such as carboxylic functions (both in the free form or esterified with glycerol), and
C=C double bonds in the fatty acid chains. In particular, the oxidative cleavage of oleic acid leads to azelaic
and pelargonic acids, that have many industrial applications.3,4 However, nowadays these are produced starting
from the purified free acid and there are no examples of procedures applied to real matrix vegetable oils. In this
work an unprecedented procedure for the direct oxidative cleavage of in fresh and exhausted vegetable oils is
presented. The oxidation has been carried out using tungstic acid as catalyst and hydrogen peroxide as a green
oxidant,5 a system already applied to the oxidative cleavage of oleic acid.6 This reaction leads to the formation
of pelargonic acid (PA) and high-azelaic glyceride (HAG in Figure 1).
Figure 1
The effects on catalysis of the composition of the vegetable oils, catalyst loading and reaction conditions will
be discussed in the poster.
[1] A. Corma, S. Iborra and A. Velty, Chem. Rev., 2007, 107, 2411-2502. [2] U. Biermann, U. Bornscheuer, M. A. Meier, J. O. Metzger and H. J. Schafer, Angew. Chem. Int. Ed., 2011, 50, 3854-3871. [3] Turnwald, S. E.; Lorier, M. A.; Wright, L. J.; Mucalo, M. R. J Mater Sci Lett 1998,17, 15, 1305-1307. [4] V. Benessere, M. E. Cucciolito, A. De Santis, M. Di Serio, R. Esposito, M. Melchiorre, F. Nugnes, L. Paduano and F. Ruffo, J. Am. Oil Chem. Soc., 2019, 96, 443-451. [5] R. Nojori, M. Aoku, K. Sato Chem. Commun., 2003, 16, 1977–1986. [6] V. Benessere, M. E. Cucciolito, A. De Santis, M. Di Serio, R. Esposito, F. Ruffo and R. Turco, J. Am. Oil Chem. Soc., 2015, 92, 1701-1707.
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Reversible Cyclometallation of Aryl-PYA Iridium Complexes Poster 16
Albert Farré*, Martin Albrecht
Departement für Chemie & Biochemie – Universität Bern, Freiestrasse 3, 3012 Bern, Switzerland, [email protected]
Classically, ligands of homogeneous catalysts have a set of intrinsic and static electronic properties that
stabilize the metal center and impart specific activity and selectivity.1 In the last decades, the development of
functional ligand motives such as Noyori’s diamine ligand2 has become a major effort in the field of
organometallic chemistry. These ligands can cooperate with the metal in a synergistic manner by undergoing
reversible structural and electronic changes during catalytic bond activation and functionalization. The effective
use of complexes bearing such non-innocent ligand systems has provided exciting catalytic applications.3 It is
interesting to note that cooperativity between the metal center and a coordinated carbon atom in chelate
complexes has not been much explored. Here, we present a set of aryl-PYA iridium complexes which can
cooperate with the metal by performing reversible cyclometallation indicated by deuterium incorporation on
the aryl moiety (see Figure 1). This process is enhanced with the introduction of electron donating substituents
on the aryl ring. These ligands may have a key role in bond activation of catalytic reactions such as water
oxidation, alcohol dehydrogenation or direct hydrogenation.
Figure 1
[1] Hartwig J. F., Organotransition Metal Chemistry, University Science Books, Mill Hill Valley, California, 2010 [2] Noyori Y. R., T. Okhuma, Angew. Chem. Int. Ed. 2001, 40, 40. [3] Khusnutdinova J. R., Milstein D., Angew. Chem. Int. Ed. 2015, 54, 12236.
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Hydrophobic Hole-Conductive Polymers for Perovskite Solar Cell Application
Poster 17
Daniele Franchi,a* Zhaoyang Yao,a Linqin Wang,a Fuguo Zhang,a Bo Xu,a Licheng Suna,b
a Department of Chemistry, KTH Royal Institute of Technology, 10044 Stockholm, Sweden. b State Key Laboratory of Fine Chemicals, DUT Dalian University of Technology, 116024 Dalian, China.
In the field of new photovoltaic technologies, Perovskite Thin Films Solar Cells represents one of the most
promising devices to enter the market in the next future.1 Since when the record efficacy of 20% has been
overcome, the scientific interest has moved to the increase of device stability and the development of materials
allowing cheaper processability during the device fabrication.2
As far as the hole-conductive material (HTM) is concerned, polymers combine chemical stability and easy
processability via inkjet or slot-die coating. Engineering the polymer structure by replacing protons with
Fluorine atoms, was proved to give rise to noncovalent interactions that 1) improve the planarity of the polymer
conjugated backbone, and 2) lower the molecular energy levels increasing the redox potentials, resulting in
improved electronic properties of the HTM.3
Here we report a library of conductive polymers based on benzodithiophene and thiophene copolymers,
functionalized with fluorine atoms, and polymerized via Stille cross coupling. The use of Stille reaction as
polymerization process allows a fine tuning of the polymer length vis temperature regulation; the
polymerization kinetics was found to be dependent on the electron density of the Pd catalyst ligands. The
halogen selectivity of the Stille protocol allowed the controlled polymerization of hetero halogenated
monomers. The solubility of the obtained polymer was regulated making use of capping agents in a three-
components coupling reaction driven by monomers electrondensity.
The obtained polymer exhibits high charge mobility, solubility in organic solvents, and good filming
properties. The photovoltaic devices built making use of the polymers shown competitive efficiencies and good
stability over time, this was addressed to the hydrophobicity of the polymeric coating, protecting the perovskite
layer from degradation due to atmospheric moisture.
[1] Jena A. K.; Kulkarni A.; Miyasakav K. Chem. Rev. 2019, 119, 3036. [2] Tress W.; Domanski K.; Carlsen B.; Agarwalla A.; Alharbi E.A.; Graetzel M.; Hagfeldt A. Nature Energy 2019. [3] Zhang Q.; Kelly M. A.; Bauer N.; You W. Acc. Chem. Res. 2017, 50, 2401.
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New (Cyclopentadienone)Iron Tricarbonyl Complexes as Pre-Catalysts for
Enantioselective Reductions of Polar Double Bonds
Poster 18
Giovanni Maria Fusi,a* Umberto Piarullia
a Università degli Studi dell’Insubria, Dipartimento di Scienza e Alta Tecnologis (DiSAT), Via Valleggio 9 – 22100
Como, Italy [email protected]
The interest in iron-based catalysts has raised in the last decade, due to the low cost and toxicity of the metal
and the availability of new robust catalysts. (Cyclopentadienone)iron tricarbonyl complexes have been recently
studied as pre-catalysts for hydrogenation and transfer hydrogenation reactions on C=O and C=N double
bonds1, since they are stable to air and moisture, unlike many other iron complexes, and they generally show
good efficiency. A new and more effective catalyst derived from the carbonylative cyclization of cyclooctyne
(complex 1a) was developed in our research group, leading to good conversions in the reduction of both
aldehydes and ketones and their imines (Figure 1 A).2 The use of (cyclopentadienone)iron tricarbonyl
complexes in enantioselective catalysis is still limited: several approaches to the preparation of stereoselective
pre-catalysts namely based on chiral substituents3 on the cyclopentadienone ring or based on the use of
complexes containing stereogenic planes4 were investigated, but only low to moderate enantioselectivity was
observed in asymmetric hydrogenation reactions. In this poster the synthesis of two new enantioselective chiral
pre-catalysts containing C2-symmetric cyclopentadienones will be presented (Figure 1 B): in both complexes
the residues influencing the stereoselectivity are placed near the reactive portion of the catalyst, in order to
possibly get better enantioselectivity.
Figure 1: A. Hydrogenation of aldehydes and ketones and transfer hydrogenation of imines catalyzed by complex 1a; B. Structure of the complexes object of our study.
[1] a) C. P. Casey, H. Guan, J. Am. Chem. Soc. 2007, 129, 5816; b) R. M. Bullock, Angew. Chem. Int. Ed. 2007, 46, 7360; c) C. P. Casey, H. Guan, J. Am. Chem. Soc. 2009, 131, 2499. [2] a) S. Vailati Facchini, J. Neudörfl, L. Pignataro, M. Cettolin, C. Gennari, A. Berkessel, and U. Piarulli, ChemCatChem 2017, 9, 1461 – 1468; b) S. Vailati Facchini, M. Cettolin, X. Bai, G. Casamassima, L. Pignataro, C. Gennari, and U. Piarulli, Adv. Synth. Catal. 2018, 360, 1054– 1059. [3] U. Piarulli, S. Vailati Facchini, L. Pignataro, Chimia International Journal for Chemistry, 2017, 71, 580-585. [4] X. Bai, M. Cettolin, G. Mazzoccanti, M. Pierini, U. Piarulli, V. Colombo, A. Dal Corso, L. Pignataro, C. Gennari, Tetrahedron 2019, 75, 1415-1424.
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45
Iridium Water Oxidation Catalysts Based on Pyridine-Carbene Alkyl-
Substituted Ligands Poster 19
Giordano Gatto,a* Ilaria Corbucci,a Francesco Zaccaria,a Helge Müller-Bunz,b Cristiano Zuccaccia,a Martin Albrecht,c and Alceo Macchionia
a Department of Chemistry, Biology and Biotechnology, University of Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy.
b School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland. c Department für Chemie und Biochemie, Universität Bern, CH−3012 Bern, Switzerland.
Iridium complexes bearing pyridine triazolylidene ligands with variable steric hindrance, derived by the
presence of an R group (R = H, Me, Et, nPr, iPr, Bu, and Oct) onto the N1-nitrogen, have been synthesized,1
characterized and tested as water oxidation catalysts (WOCs),2 using chemical sacrificial oxidants (CAN and
NaIO4) or in photocatalytic experiments ([Ru(bpy)3]Cl2 as phosensitizer
and Na2S2O8 as an electron acceptor). Those complexes and similar ones
with N,C or C,C -bidentate triazole-derived carbene ligands appear to be
particularly suited to explore ligand tailoring due to their generally high
productivity and preserved molecular nature under typical WO reaction
conditions.3,4,5 The catalytic activity is not particularly affected by the size
of 1-R when WO is driven by NaIO4 (1 min-1 < TOF < 14 min-1) or
light/[Ru(bpy)3]Cl2/Na2S2O8 (TOF ≈ 0.15 min-1); on the contrary, a
remarkable effect is observed with CAN. In the latter case, complexes with R = H and Me exhibit similarly low
activity (10 min-1 < TOF < 20 min-1), whereas all other complexes are significantly more active and exhibit
comparable TOFs in the range 40-130 min-1. Thus, a discontinuity in performances occurs when passing from
R = Me to R = Et. It appears plausible that the steric hindrance introduced in close proximity of the iridium
center, when R ≥ Et, hampers transfer of the hydroperoxo or peroxo moiety from iridium active species to
cerium, a process that could slow down kinetics of O2 evolution.6
[1] Corbucci, I.; Petronilho, A.; Müller-Bunz, H.; Rocchigiani, L.; Albrecht, M.; Macchioni, A. ACS Catal. 2015, 5, 2714–2718. [2] Macchioni, A. Eur. J. Inorg. Chem. 2019, 7-17. [3] Lalrempuia, R.; McDaniel, N. D.; Müller-Bunz, H.; Bernhard, S.; Albrecht, M. Angew. Chem. Int. Ed. 2010, 49, 9765 –9768. [4] Petronilho, A.; Rahman, M.; Woods, J. A.; Al-Sayyed, H.; Müller-Bunz, H.; Don MacElroy, J. M.; Bernhard, S.; Albrecht, M. Dalt. Trans. 2012, 41 (42), 13074–13080. [5] Vivancos, Á.; Segarra, C.; Albrecht, M. Chem. Rev. 2018, 118 (19), 9493–9586. [6] Bucci, A.; Menendez Rodriguez, G.; Bellachioma, G.; Zuccaccia, C.; Poater, A.; Cavallo, L.; Macchioni, A. ACS Catal. 2016, 6 (7), 4559–4563.
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46
Chemoselective Addition of Organolithium Reagents to Arylcarboxamides in
Cyclopentyl Methyl Ether en Route to Aromatic Ketones Poster 20
Simone Ghinato,a* Vito Capriati,b Marco Blangetti,a Cristina Prandia
aDipartimento di Chimica, Università degli Studi di Torino, via P. Giuria 7, I-10125 Torino, Italy. bDipartimento di Farmacia–Scienze del Farmaco, Università di Bari “A. Moro”, Consorzio C.I.N.M.P.I.S., Via E. Orabona 4, I-70125
Bari, Italy. [email protected]
Nucleophilic addition of organometallics to carboxamides is a fundamental reaction for the synthesis of
ketones widely employed both in academia and industry. The major challenge associated with this protocol is
the over-addition taking place when highly polarized organometallic reagents (like organolithium and Grignard
reagents) are used, with the result of the formation of tertiary alcohols as the major adducts because of the low
stability of the tetrahedral intermediates.1 Significative advances have been achieved throughout the years by
using chelating Weinreb amides,2 ketone-like-reactive N-acylpyrroles3 and pyramidalized non-planar N-
acetylazetidine4 as well as by exploiting the Charette electrophilic activation.5 Increasingly, stringent
environmental legislation and urgent action to address the climate crisis have generated a pressing need for
cleaner methods of chemical production.6 Buiding on our recent findings in metal-mediated organic
transformations in deep eutectic solvents as nonconventional and bio-renewable reaction media,7 in this
communication we first report the 1,2-addition of organolithium reagents to simple, tertiary alkyl/aryl
carboxamides in the eco-friendly cyclopentyl methyl ether (CPME).8 Notable features of our report are: (a) the
suppression of over-addition byproducts, (b) mild and scalable reaction conditions (room temperature, open
air), (c) short reaction times (within seconds) and (d) solvent recycling.
[1] Luisi, R.; Capriati, V. Lithium Compounds in Organic Synthesis; Wiley-VCH: Weinheim, 2015. [2] Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815. [3] Evans, D. A.; Borg, G.; Scheidt, K. A. Angew. Chem. Int. Ed. 2002, 41, 3188. [4] Chengwei, L.; Achtenhagen, L.; Szostak, M. Org. Lett. 2016, 18, 237. [5] Bechara, W. S.; Pelletier, G.; Charette, A. B. Nat. Chem. 2012, 4, 228. [6] Sheldon, R. A. Green Chem. 2007, 9, 1273. [7] Ghinato, S.; Dilauro, G.; Perna, F. M.; Capriati, V.; Blangetti, M.; Prandi, C. Chem. Commun. 2019, 55, 7741. [8] Azzena, U.; Carraro, M.; Pisano, L.; Monticelli, S.; Bartolotta, R.; Pace, V. ChemSusChem 2019, 12, 40.
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Study of the Interaction Between Ionic Liquids and Phospholipid Bilayers by
Atomic Force Microscopy Poster 21
Matteo Giannangeli,a* Anna Moronib, Alessandro Casellia, Alessandro Podestàc
a Dip. Chimica, Univ. degli Studi, via Golgi 19 – 20133 Milano, Italy. b Dip. Bioscienze, Univ. degli Studi, via Celoria 26 – 20133 Milano, Italy. c CIMaINa and Dip. Fisica “Aldo Pontremoli”, Univ. degli Studi, via Celoria 16 – 20133
Milano, Italy. [email protected];
Supported phospholipid bilayers exposed to molecules and nanoparticles (including proteins) from a
suitable liquid medium can be considered as a simplified model for studying basic interaction mechanisms of
biomembranes with their microenvironment, in living systems. This biomimetic model is suitable to study
membrane protein channels, as well as the toxicity of molecules; in both cases, the interaction is likely to
induce changes of the structural and mechanical properties of the biomembrane, which can be measured by
means of suitable nanoscale tools. Ionic liquids (ILs) are salts that are generally liquid at room temperature.1
Because of their negligible vapor pressure, controlled miscibility, and versatility in designing the molecular
structure, they are considered “green solvents”,2 and are recently replacing volatile organic solvents in several
large scale industrial synthesis processes.3 However, despite their “green” reputation, ILs have a certain level
of toxicity, confirmed by several studies, mainly based on EC50 values.4 The aim of this work was to investigate
the mechanisms involved in the cytotoxicity of imidazolium-based [Bmim][Cl] and [Omim][Cl] ionic liquids
(Figure 1) by means of Atomic Force Microscopy (AFM), using supported phospholipidic bilayers to mimic
the cell membrane. AFM was used to probe the rigidity and the structural cohesion of the lipid membrane upon
interaction with the ILs, via force versus indentation analysis,5 as well as to characterize the interaction force
of model alkyl chains with the lipid membrane. To this
aim, a synthesis protocol was developed for the
functionalization of AFM probes.
Our results show that ILs are able to induce significant
structural changes in the lipid membrane, with
potentially toxic effects even at low doses. Moreover,
force spectroscopy experiments suggest that the alkyl
chain of ILs strongly interact with the bilayer, possibly
by tail-first insertion into the phospholipid bilayer.
Acknowledgements. noMAGIC project, “Noninvasive Manipulation of Gating in Ion Channels” Project ID: 695078 Funded under: H2020-EU.1.1. – EXCELLENT SCIENCE – European Research Council (ERC).
[1] N. Jain, A. Kumar, S. Chauhan, S. M. S. Chauhan, Tetrahedron 2005, 61, 1015–1060. [2] J. P. Hallett, T. Welton, Chem. Rev. 2011, 111, 3508–3576. [3] S. G. Cull, J. D. Holbrey, V. Vargas-Mora, K. R. Seddon, G. J. Lye, Biotechnol. Bioeng. 2000, 69, 227–233. [4] A. Romero, A. Santos, J. Tojo, A. Rodríguez, J. Hazard. Mater. 2008, 151, 268–273.
POSTERS
Figure 1. a) detail of the AFM probe scanning the sample b) chemical structure of 1-Butyl-3-methylimidazolium Chloride [Bmim][Cl] and 1-octyl-3-methylimidazolium chloride [Omim][Cl]
N
N
Cl
N
N
Cl
[Bmim][Cl]
[Omim][Cl]
a) b)
48
New Tools for The Synthesis of Metalloporphyrins
Poster 22
Carla Gomes,a* Marta Pineiroa
a CQC and Department of Chemistry, Rua Larga 3049-535, Coimbra, Portugal.
Metalloporphyrins are keystones for biochemical, enzymatic and photochemical processes, which are
fundamental for the existence of life. Metalloporphyrins are the central compounds in many applications related
with sustainable chemistry, such as oxidation catalysis or methanogenesis.1
The synthesis of metalloporphyrins for these applications was traditionally made by insertion of the metal
into the tetrapyrrolic macrocycle using large excess of organic or inorganic bases, metal salts and chlorinated
or high boiling point organic solvents.2 Therefore, using methodologies far from the green chemistry ideals.3
New tools for organic chemistry based on novel activation techniques such as microwave irradiation, ultrasound
or mechanical activation open the way to the development of new methodologies with optimized characteristics
from the green chemistry point of view with high efficiency, low energy consumption and minimal waste
production. Herein we present the green synthesis of metalloporphyrins of the first period of transition metals
and group 10 of the periodic table using mechanochemical or ultrasound activation. (Figure 1).
Figure 1
[1] Shao, S.; Rajendiran, V.; Lovell, J. F. Coord. Chem. Rev. 2019, 379, 99–120; Calvete, M. J. F.; Pineiro, M.; Dias, L. D.; Pereira, M. M. ChemCatChem 2018, 10, 3615–3635; Pereira, M. M.; Dias, L. D.; Calvete, M. J. F. ACS Catal. 2018, 8, 10784–10808. [2] Smith, K. M. Porphyrins and Metalloporphyrins; Elsevier: Amsterdam, 1975; Pineiro, M. Curr. Org. Syn., 2014, 11, 89-109. [3] Anastas, P.; Eghbali, N. Chem. Soc. Rev. 2010, 39, 301-312.
Acknowledgements: CQC is supported by FCT, through the project Nº 007630 UID/QUI/00313/2013, co-funded by COMPETE2020-UE. The authors also thank the UC-NMR facility for NMR spectroscopic data (www.nmrccc.uc.pt). C. G. thanks FCT- CATSUS PhD Program (PD/BD/135531/2018).
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Radiolabeled Au(III) N-Heterocyclic Carbenes (NHC) for in vivo Imaging
Poster 23
Federica Guarra,a* Tarita Biver,a,b Chiara Gabbiani,a Ennio Zangrando,c Luca Salassa,d Jordi Llop,e Alessio Terenzid
a Department of Chemistry and Industrial Chemistry, Via G. Moruzzi 13, 56124 Pisa (PI), Italy. b Department of
Pharmacy, Via Bonanno Pisano 12 56126, Pisa (PI), Italy. cDepartment of Chemical and Pharmaceutical Sciences, Via L. Gorgieri 1, 34127 Trieste (TS), Italy. d Donostia International Physics Center, Manuel Lardizabal Ibilbidea 4, 20018
Donostia, Gipuzkoa, Spain. e CIC BiomaGUNE, Miramon Pasealekua 182, 20014 Donostia, Gipuzkoa, Spain. [email protected]
Gold complexes with N-heterocyclic carbenic ligands (NHCs) have found application in both catalysis and
medicinal chemistry. High stability in solution and straightforward synthesis render gold(I) NHCs particularly
attractive as anticancer drug candidates. Moreover, substituents on the NHC ring can be modified to fine tune
biological and tumor targeting properties. Preclinical studies on gold(I) NHCs showed potent antiproliferative
activity in vitro and in vivo. Despite being less investigated, gold(III) NHCs are also reported to have promising
anticancer properties.1,2 However, it is still debated whether and how the gold(III) center plays an active role in
the observed biological activity.1,3 Overall gold NHCs showed a mechanism of action that differs from platinum
approved drugs, offering the possibility for innovative therapeutic strategies.1-3
Within this frame, we synthesized a series of gold(III) NHCs and developed a radiolabeling strategy via
direct oxidation with radioactive iodine (Figure 1). The biodistribution in vivo has been investigated with PET
imaging experiments on rats. This could represent a valuable tool to gain insights into the in vivo stability of
non cyclometalated gold(III) complexes.
Figure 1
[1] Porchia, M., Pellei, M., Marinelli, M., Tisato, F., Del Bello, F., Santini, C., Eur. J. Med. Chem., 2018, 146, 709. [2] Lok, C.-N., Zhanga, J.-J., Che, C.-M., Chem. Soc. Rev., 2015, 44, 8786. [3] Zou, T, Lum, C.T., Chui, S. S-Y., Che, C.-M., Angew. Chem. Int. Ed., 2013, 52, 2930.
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50
[OSSO]-Type Iron (III) Complexes for Ring Opening Polymerization of Cyclic
Esters
Poster 24
Salvatore Impemba,a Francesco Della Monica,a Carmine Capacchione,a,b Alfonso Grassi,a,b Stefano Milionea,b
a Department of Chemistry and Biology, University of Salerno, via Giovanni Paolo II, 132 Fisciano I-84084, Salerno,
Italy. b Interuniversity Consortium Chemical Reactivity and Catalysis, CIRCC, via Celso Ulpiani 27, 70126 Bari, Italy. [email protected]
Nowadays, about 350 million of tons of plastics are produced annually all over the world and most
of these plastics are of petroleum origin. The environmental and economic problems related to the
petrochemical-derived polymers have driven the academic research toward the development of green
and degradable alternatives to conventional plastics.1 The biodegradable polymers, for example
aliphatic polyesters, can be considered safe for the environment and an interesting alternative to
conventional polymers. One of the most efficient methods to synthesize aliphatic polyesters, such as
polylactic acid and poly-b-hydroxybutyrate, is the ring opening polymerization (ROP) of cyclic esters
initiated by coordination compounds.2 In literature many metal based complexes have been reported
to promote this reaction but few of these are based on iron although this element is widely available,
cost effective and non-toxic. This work explores the catalytic performances of an iron complex
featuring a tetradentate (OSSO)-type bis(phenolato) ligand3 in ring opening polymerization of rac-
lactide, β-butyrolactone and caprolactone. The activities compares well with those reported for most
active iron complexes.4 Interestingly, the MALDI-TOF-MS investigations on the resulting polymeric
structures revealed the highly selective formation of cyclic polymers.
Figure 1
[1] S. Kubowicz , A. M. Booth, Environ. Sci. Technol., 2017, 51, 12058-12060. [2] Dechy-Cabaret, B. Martin-Vaca, D. Bourissou, Chem. Rev., 2004, 104, 6147–6176. [3] F. Della Monica, B. Maity, T. Pehl, A. Buonerba, A. De Nisi, M. Monari, A. Grassi, B. Rieger, L. Cavallo, C. Capacchione, ACS Catalysis, 2018, 8, 6882-6893. [4] M. Cozzolino, V. Leo, C. Tedesco, M. Mazzeo, M. Lamberti, Dalton Trans., 2018, 47, 13229–13238.
POSTERS
51
Hydrogenation and Dehydrogenation Reactions with Asymmetric Bimetallic
Rh-Rh or Rh-Pt Complexes
Poster 25
Pascal Jurt,a* Anne S. Abels,a Thomas L. Gianetti,b Hansjörg Grützmacherb
a ETH Zurich, Vladimir-Prelog-Weg 1, 8049 Zürich, Switzerland. b University of Arizona, Tucson, 1306 E. University Blvd., 86721-0041 Tucson (Az), USA.
Figure 1
Bimetallic transition metal complexes have been investigated heavily in the 70’s and 80’s of the last century1
and the interest in such complexes has recently seen a renaissance.2 Many of these bimetallic systems
outperform monometallic compounds in terms of activity, selectivity, functional group tolerance and catalyst
loading.3, 4 We designed ligand scaffold 1, which allows (i) to bind two metal centers in close proximity, and
(ii) is especialy suited to stabilize low valent metal centers. Two examples are the homobimetallic [Rh,Rh]
complex 25 and the heterobimetallic [Rh,Pt] complex 3 (Figure 1 a).
These catalysts perform very well in hydrogenation and dehydrogenation reactions. Remrakably, 2 is a
highly active and selective catalyst for the dehydrogenation of aminoborane forming borazine (Figure 1 b).
Complex 3 is active but less selective than 2. However, 3 is a good catalyst for the hydrogenation of nitrous
oxide, a kinetically inert molecule and a potent greenhouse gas (Figure 1 c).6
[1] H. Vahrenkamp, Angew. Chem. Int. Ed., 1978, 17, 379-392. [2] J. F. Berry and C. M. Thomas, Dalton Trans., 2017, 46, 5472-5473. [3] M. K. Karunananda and N. P. Mankad, ACS Catal., 2017, 7, 6110-6119. [4] M. E. Broussard, B. Juma, S. G. Train, W.-J. Peng, S. A. Laneman and G. G. Stanley, Science, 1993, 260, 1784-1788. [5] P. Jurt, O. Salnikov, T. L. Gianetti, N. Chukanov, M. G. Baker, G. Le Corre, J. E. Borger, R. Verel, S. Gauthier, O.
Fuhr, K. V. Kovtunov, A. Fedorov, D. Fenske, I. V. Koptyug and H. Grützmacher, Chem. Sci., 2019, DOI: 10.1039/C9SC02683E.
[6] J. Hansen and M. Sato, Proceedings of the National Academy of Sciences of the United States of America, 2004, 101, 16109-16114.
POSTERS
52
Catalytic Activity of Carbon Supported Cu(I) Complexes for the Synthesis of
1,2,3-Triazoles
Poster 26
Ivy L. Librando,a* Abdallah G. Mahmoud,a Sónia A.C. Carabineiro,a Carlos F.G.C. Geraldes,b M. Fátima C. Guedes da Silva,a Armando J.L. Pombeiroa
a Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001
Lisboa, Portugal. b Faculdade de Ciências e Tecnologia, Universidade de Coimbra, Calçada Martim de Freitas 3000-393 Coimbra, Portugal.
Cu(I) halide complexes were synthesized according to the literature.1 Different carbon materials (activated
carbon and multi-walled carbon nanotubes) with three different surface treatments (shown in Scheme 1,
pristine; oxidized with nitric acid-ox; and oxidized with nitric acid and afterwards with NaOH-oxNa) were
prepared according to previous publications.2-7 Complexes were immobilized on the carbon materials, as in
previous works,2-7 and used as recyclable catalysts for the synthesis of disubstituted triazoles (Scheme 2), as in
literature.8,9 Catalytic performance of the heterogenized catalysts shows excellent yields than their
homogeneous counterparts and further increased upon the use of CNT (carbon nanotube) materials as support.
Moreover, the reaction was performed under MW irradiation for 15 min at lower temperature (80 0C) with very
low catalyst loading of 0.067 mol %.
Scheme 1. Functionalization of carbon nanotubes (CNT).
Scheme 2. Preparation of 1,2,3-triazoles using C/Cu(I) complexes.
[1] Mahmoud, A.G.; Guedes da Silva, M.F.C.; Sokolnicki, J.; Smolenski, P.; Pombeiro, A.J.L. Dalton Trans. 2018, 47, 7290-7299. [2] de Almeida, M.P.; Martins, L.M.D.R.S.; Carabineiro, S.A.C.; Lauterbach, T.; Rominger, F.; Hashmi, A.S.K.; Pombeiro, A.J.L.; Figueiredo, J.L. Catal. Sci. Technol. 2013, 3, 3056–3069. [3] Martins, L.M.D.R.S.; de Almeida, M.P.; Carabineiro, S.A.C.; Figueiredo, J.L.; Pombeiro, A.J.L. ChemCatChem 2013, 5, 3847–3856. [4] Sutradhar, M.; Martins, L.M.D.R.S.; Carabineiro, S.A.C.; Guedes da Silva, M.F.C.; Buijnsters, J.C.; Figueiredo, J.L.; Pombeiro, A.J.L. ChemCatChem 2016, 8, 2254–2266. [5] Wang, J.; Martins, L.M.D.R.S.; Ribeiro, A.P.C.; Carabineiro, S.A.C.; Figueiredo, J.L.; Pombeiro, A.J.L., Chem. Asian J. 2017, 12, 1915–1919. [6] Carabineiro, S.A.C.; Martins, L.M.D.R.S.; Pombeiro, A.J.L.; Figueiredo, J.L., ChemCatChem 2018, 10, 1804–1813. [7] Martins, L.M.D.R.S.; Ribeiro, A.P.C.; Carabineiro, S.A.C.; Figueiredo, J.L.; Pombeiro, A.J.L., Dalton Trans. 2016, 45, 6816–6819. [8] Nia, A.S. et al. Chem. Eur. J. 2015, 21, 10763-10770. [9] Mahmoud, N.; Jaleh, B.; Fakhri, P.; Zahraei, A.; Ghadery, E., RSC Adv. 2015, 5, 2785-2793. Acknowledgement: I.L.L. acknowledges financial support from CATSUS PhD grant PD/BD 135555/2018. Support for this work was also provided by FCT through project UID/QUI/00100/2019.
POSTERS
53
Complexes of Homo- and Heteroditopic NHC Ligands: Equilibria in Solution
and Luminescence Studies Poster 27
Andrea Longhi,a* Marzio Rancan,b Gregorio Bottaro,b Lidia Armelao,a,b Claudia Graiff, c Cristina Tubaroa
aDipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy. b Istituto di Chimica della Materia Condensata e di Tecnologie per l’Energia, ICMATE-CNR, via Marzolo 1, 35131 Padova, Italy. cDipartimento di Scienze Chimiche, Della Vita e della Sostenibilità Ambientale, Università degli Studi di Parma, Parco
Area delle Scienze 17/A, 43124, Parma, Italy. [email protected]
Metal complexes with multidentate N-heterocyclic carbene (NHC) ligands are nowadays studied for several
applications (catalysis, luminescent materials, medicinal chemistry, sensing).1 The majority of the examples reported in literature deals with di(NHC) ligands based on imidazol-2- ylidene
rings. Recently, also heteroditopic di(NHC) i.e. ligands with two different types of carbene moieties, like
imidazol-2-ylidene and 1,2,3- triazol-5-ylidene (nNHC/tzNHC), have been studied.2 Here, the synthesis and
properties (luminescence and dynamic behaviour in solution) of homo- and heterobimetallic complexes
(M=Ag(I), Au(I), Pd(II)) with nNHC/tzNHC ligands will be illustrated (Figure 1). In the gold(I) homobimetallic complexes, the distance between the two metal centres can be lower than the
sum of their van der Waals radii, thus suggesting the presence of aurophilic interaction, which is correlated to
emission properties.3 In this regard, the use of a bidentate ligand with a N-N bond between the two heterocycles,
such as di(1,2,4-triazol-5-ylidene), is appealing; it should in fact force the metal centres close to each other.4
The homometallic Ag(I) and Au(I) complexes with this ligand and their equilibria in acetonitrile will be also
presented.
Figure 1
[1] Mercs, L.; Albrecht, M. Chem. Soc. Rev. 2010, 39, 1903. [2] Monticelli, M.; Baron, M.; Tubaro, C.; Bellemin-Laponnaz, S.; Graiff, C.; Bottaro, G.; Armelao, L.; Orian, L. ACS Omega 2019, 4 (2), 4192. [3] Baron, M; Tubaro, C.; Biffis, A.; Basato, M.; Graiff, C.; Poater, A.; Cavallo, L.; Armaroli, N.; Accorsi, G. Inorg. Chem. 2012, 51, 1778. [4] Poyatos, M.; McNamara, W.; Incarvito, C.; Peris, E.; Crabtree, R. H. Chem. Commun. 2007, 2267.
POSTERS
54
Hetero / Homometallic Coinage Metals’s Trinuclear Metallocycles: a New Route
for their Synthesis
Poster 28
Lorenzo Luciani,a* Mohammad A Omary,b Rossana Galassia
a School of Science and Technology, Via S. Agostino 1, 62032 Camerino (MC), Italy. b Department of Chemistry,
University of North Texas, Denton, TX 76203, USA. [email protected]
Homonuclear Coinage metals Trinuclear metalloCycles (CTC) are a class of C, N coordination compounds
that are known since 1970’s.1 Their synthesis proceeds by the proton abstraction from the azolate and
subsequent metalation with proper metal sources or rearrangement of nitriles to carbeniate in basic
environment. The homonuclear compounds exhibit sophisticated emissive, molecular recognition,
metalloaromaticity properties, but the interest on these compounds was recently renewed because their
unprecedented optoelectronic properties such as near unit quantum yield,2 VOC adsorption3 and their
application in OLED. By mixing solutions of CTC with different metals and different ligands heterobimetallic
CTCs are obtained as well as pi-pi stacking supramolecular structures. Heterobimetallic Ag/Au and Cu/Au
compounds are strongly luminescent showing both fluorescence and phosphorescence phenomena in both the
solid and solution states (Figure 1).
Figure 1. The plot shows the CTCs mixing in THF solution of [Ag(µ-1-Vinim)2]3 / [Au(µ-1-Benzylim)2]3 by
fluorescence spectroscopy, upon excitacion at 310 nm. After 2 h a strong increase of the emission intensity at 350 nm
indicates the formation of Au/Ag CTC. On the right, the high intensity emission of the solid state is showed.
[1] a) Bonati, F., Minghetti, G Angew. Chem., Int. Ed. 1972, 11, 429. b) Vaughan, L. G. J. Am. Chem. Soc. 1970, 11, 730. [2] Galassi, R., Ghimire, M.M., Otten, B.M., Ricci, S., McDougald, R.N., Almotawa, R.M., Alhmoud, D., Ivy, J.F., Rawashdeh, A.-M.M., Nesterov, V.N., Reinheimer, E.W., Daniels, L.M., Burini, A., Omary, M.A. PNAS, 2017, 114 (26), E5042. DOI: 10.1073/pnas.1700890114 [3] Galassi, R., Ricci, S., Burini, A., Macchioni, A., Rocchigiani, L., Marmottini, F., Tekarli, S.M., Nesterov, V.N., Omary, M.A. Inorg. Chem., 2013, 52 (24), 14124. DOI: 10.1021/ic401948p
POSTERS
55
Tuning the Catalytic Activity of N-Heterocyclic Carbene Iron Piano Stool Complexes
Poster 29
Pamela V. S. Nylund,a* Martin Albrechta
a Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, CH-3012 Bern, Switzerland. [email protected]
Industrial hydrosilylation is mainly catalysed by precious platinum group metals. However, these scarce
metals have a high environmental impact and are expensive and toxic. One current challenge is to replace them
by environmentally friendly base metal systems, which ideally maintain high selectivity, activity and
longevity.1 1 In recent years, N-heterocyclic carbene iron(II) piano stool complexes have emerged as catalysts
for hydrosilylation of carbonyls. Both imidazolylidene and triazolylidene iron(II) complexes have proven to be
active in this type of reaction.2 2
Figure 1
Herein we present a comparison between different NHC iron(II) piano stool complexes and discuss their
differences in catalytic hydrosilylation reactions. Specifically, we varied the type of carbene (imidazolylidene
vs triazolylidene skeleton), the wingtip groups R and the stabilising spectator ligand (Cp vs Cp*) to identify
the catalytically most active system.
[1] Hofmann, R. J.; Vlatkovic, M.; Wiesbrock, F. Polymers (Basel). 2017, 9 (10), 534. [2] Johnson, C.; Albrecht, M. Organometallics 2017, 36 (15), 2902–2913.
POSTERS
56
Synthesis of Diverse Classes of Thiahelicenes by Transition Metal-Catalysed
Cross Coupling Reactions Poster 30
Valentina Pelliccioli,a* Silvia Cauteruccio,a Emanuela Licandroa
a Dipartimento di Chimica, Università degli Studi di Milano, Golgi 19, 20133, Milan, Italy. [email protected]
Tetrathia[7]helicenes (7-THs) are an attractive class of polyconjugated ortho-fused heteroaromatic
compounds, endowed with inherent chirality due to the helical shape of their π-conjugated system.1 Their
unique structural and chiroptical properties have stimulated manifold studies in optoelectronics,2 catalysis,3 and
biology.4 In our ongoing studies on the synthesis and functionalization of 7-TH systems, we have recently
developed an innovative diversity-oriented synthesis of 7-THs exploiting transition metal-catalysed cross
coupling reactions as key steps (Figure 1).5
Figure 1
In this communication we report the synthesis of novel classes of thiahelicenes 1a-c starting from the key
intermediates 2, from which we can obtain: i) helicenes 1a through Sonogashira coupling with terminal alkynes,
followed by In- or Pt-catalysed intramolecular hydroarylation of alkynes 3; ii) helicenes 1b through palladium-
catalysed annulation of 2 with internal alkynes; iii) helicenes 1c through Suzuki coupling with (hetero)aryl
boronic esters, followed by oxidative photochemical cyclization of intermediates 4.
[1] Licandro, E.; Cauteruccio, S.; Dova, D. Adv. Heterocycl. Chem. 2016, 118, 1. [2] Bossi, A.; Licandro, E.; Maiorana, S.; Rigamonti, C.; Righetto, S.; Stephenson, G. R.; Spassova, M.; Botek, E.; Champagne, B. J. Phys. Chem. C 2008, 112, 7900. [3] Cauteruccio, S.; Dova, D.; Benaglia, M.; Genoni, A.; Orlandi, M.; Licandro, E. Eur. J. Org. Chem. 2014, 2694. [4] Cauteruccio, S.; Bartolini, C.; Carraro. C.; Dova, D.; Errico, C.; Ciampi, G.; Dinucci, D.; Chiellini, F., Licandro, E. ChemPlusChem. 2015, 80, 490. [5] Cauteruccio, S.; Pelliccioli, V.; Licandro, E. Manuscript in preparation.
POSTERS
57
Synthesis of Hybrid Materials for Potential Degradation of Antibiotics Poster 31
G. Piccirillo,a* M. M. Pereira,a J. P. C. Tomé,b M. E. S. Eusébio,a M. J. F. Calvetea
a CQC, Departamento de Química Universidade de Coimbra, Rua Larga, 3004-535 Coimbra, Portugal. b CQE,
Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal [email protected]
Since 1928, when Fleming discovered the penicillin, hundreds of other antibiotics have been produced and
have played an essential role in humans and animals to treat infectious diseases, to improve animal feed
efficiency, having significantly improved public health.1 During this period the bacterial resistance has grown,
existing a strong link between it and antibiotics consumption and, as result, the treatments of various infections
have become less efficient worldwide.2 Significant concentrations of these pharmaceuticals have been found in
the environment, for instance in groundwater, via human urinary or fecal excretion, and nowadays, this
represents a major problem, being a potential risk for biological organisms and ecosystems. The global
apprehension has directed the research towards non-biological processes for the destruction of these pollutants
in waters, and particularly the focus is currently on advanced oxidation processes (AOP)s.3 The final goal of
these technologies is to oxidize the contaminants in more simple, harmless inorganic molecules through the “in
situ” production of hydroxyl radicals.4 Metal-complexes of tetrapyrrolic macrocycles are described as powerful
oxidation catalysts in a variety of reactions,5-7 including in the degradation of organic pollutants (e.g.
pesticides). Considering this knowledge, it is our intention to develop hybrid material based on these molecules
to promote potential sustainable degradation processes by using hydrogen peroxide as non-toxic oxidant. In
this communication, we present our recent achievements on the synthesis of manganese complexes of
tetrapyrrole-based catalysts and their structure-property relationship study on the degradation of antibiotics,
namely trimethoprim.
Figure 1: Degradation of
antibiotics in water matrix by
using tetrapyrrolic based
catalysts.
Acknowledgements: We thank the Fundação para a Ciência e Tecnologia (FCT) and FEDER (European Regional Development Fund)
for financial support with UID/QUI/00313/2019 and POCI-01-0145-FEDER-027996. G.P. also thanks the FCT and CATSUS program
for her PhD grant (PD/BD/135532/2018).
[1] S. Pareek, N. Mathur, A. Singh, A. Nepalia, Int.J.Curr.Microbiol.App.Sci, 2015, 4, 278. [2] WHO Report on Surveillance of Antibiotic Consumption 2016 – 2018 Early implementation, https://www.who.int/medicines/areas/rational_use/who-amr-amc-report-20181109.pdf . Last access: 18/07/2019. [3] M. J. F. Calvete, G. Piccirillo, C. S. Vinagreiro, M. M. Pereira, Coord. Chem. Rev., 2019, in press. [4] O. Gonzalez, C. Sans S. Esplugas, J. Hazard Mater., 2007, 146, 459. [5] M. M. Pereira, L. D. Dias, M. J. F. Calvete, ACS Catal., 2018, 8, 10784. [6] S. M. A. Pinto, C. S. Vinagreiro, V. A. Tomè, G. Piccirillo, L. Damas, M. M. Pereira, JPP, 2019, 23, 1. [7] L. Fernández, V. I. Esteves, Â. Cunha, R.J. Schneider, J.P.C. Tomé, J. Porphyr. Phthalocyanines, 2016, 20, 150.
POSTERS
58
Gold-Catalyzed Cascade Reactions of 4H‐Furo[3,2‐b]Indoles with Allenamides:
Synthesis of Indolin-3-one Derivatives
Poster 32
Valentina Pirovano,a* Elisa Brambilla,a Giorgio Abbiati,a Elisabetta Rossia
a Dipartimento di Scienze Farmaceutiche, Sezione di Chimica Generale e Organica “A. Marchesini, Università degli
Studi di Milano (Italy). [email protected]
2-Spirocyclopentane-1,2-dihydro-3H-indol-3-ones (namely, spiropseudo-indoxyls) constitute privileged
scaffolds in organic synthesis and represent core components of different indole alkaloids (e.g. aristotelone and
brevianamide A)1 and of molecules applied as functional dyes.2 In addition, they have found also an application
as useful intermediate in the total synthesis of minfiensine.3 Taking into account these premises and our
expertise in gold-catalyzed indole functionalization,4,5 we tested the reactivity of 4H-furo[3,2-b]indoles in the
presence of electrophilic gold(I) activate π-systems (allenamides) with the aim to develop a new cascade
process for the synthesis of these relevant scaffolds (Scheme 1).6 In this poster we present the obtained results
together with the scope and limitation of the method and the proposed reaction mechanism.
Scheme 1
[1] Williams, R. M.; Cox, R. J. Acc. Chem. Res. 2003, 36, 127. [2] Chen, H.; Shang, H.; Liu, Y.; Guo, R.; Lin, W. Adv. Funct. Mater. 2016, 26, 8128. [3] Yu, Y.; Li, G.; Jiang, L.; Zu, L. Angew. Chem. Int. Ed. 2015, 54, 12627. [4] Pirovano, V. Eur. J. Org. Chem. 2018, 1925. [5] Rossi, E.; Pirovano, V.; Abbiati, G. Eur. J. Org. Chem. 2017, 4512. [6] Pirovano, V.; Brambilla, E.; Rizzato, S.; Abbiati, G.; Bozzi, M.; Rossi, E. J. Org. Chem. 2019, 84, 5150.
N
O
RNR
O
Planned gold-catalyzed cascade reaction
N
O
R
a) C-2 addition; b) ring-opening; c) ring-closing
N
O
R
abc
[Au] [Au]
[Au]
Spiropseudo-indoxyl
N
O
CO2Et
NMe
EWGR2
[Au(IPr)NTf2] (5 mol%)CH2Cl2, -20 °C
R1 NCO2EtR1
O
Me
NR2
EWG
13 examples45-77%
POSTERS
59
In Situ Prepared Nickel Boride Catalyzed Reduction of Azides with and without
Nanocellulose Support
Poster 33
Giampiero Proietti,a* Peter Dinéra
a Department of Chemistry, KTH-Royal Institute of Technology, Teknikringen 30, SE-10044 Stockholm Sweden, [email protected]
Herein is presented a mild and green catalytic reduction of aromatic and aliphatic azides to form the
corresponding primary amines using catalytic amounts of nickel boride. The starting catalyst system involves
the in-situ formation of the active catalyst from nickel chloride and NaBH4 in which NaBH4 also acts as the
stoichiometric reducing agent. Whilst the majority of the reported protocols for the metal assisted NaBH4
reduction of azides make use of stoichiometric amount of the metal,1 in this work, an optimization of the
reaction conditions allowed to minimize the catalyst loading of the metal (NiCl2) down to 0.5 mol% (Figure 1).
Figure 1
A tandem protocol was also developed in which the formed amines were in situ BOC-protected. In addition,
the ability of loading the catalyst on a nanocellulose support was exploited in order to facilitate the removal of
the catalyst from the reaction mixture and recycle it for a new azide reduction.
[1] Ganem, B.; Osby, J. O. Chem. Rev. 1986, 86, 763.
POSTERS
60
Copper-catalysed C–N Coupling Reactions with no Additional Ligands for
Ullmann Amine Synthesis in Deep Eutectic Solvents Poster 34
Andrea F. Quivelli,a* Paola Vitale,a Filippo M. Perna,a Vito Capriati a
aDipartimento di Farmacia-Scienze del Farmaco, Università degli Studi di Bari "Aldo Moro”, Consorzio C.I.N.M.P.I.S,
Via E. Orabona 4, 1-70125 Bari, Italy; [email protected]
Many efforts are currently being made to replace extensively used hazardous volatile organic solvent
(VOCs) in favour of “greener”, inexpensive and recyclable reaction media (e.g., water, Deep Eutectic Solvents
(DESs)).1,2 DESs represent an emerging generation of unconventional solvents generally composed of two or
three safe, inexpensive and nature-inspired components able to engage in reciprocal hydrogen-bond interactions
to form a eutectic mixture with a melting point much lower than that of the individual components. Recent
breakthroughs by our research group3-5 and others6,7 have shown that show metal-catalysed and metal-mediated
organic reactions can be successfully run both in DESs and in water. Copper-catalysed organic reactions are
especially attractive because they make use of cheaper and environmentally responsible first-row transition
metals.8 Copper-catalysed Ullmann-type C–N coupling reactions, in particular, proved to be useful for the
synthesis of N-functionalised aryl and (hetero)aryl compounds starting from aryl halides and amines. These
reactions are usually carried out in VOCs (e.g., THF, toluene),9 at high temperature, and in the presence of
ligands.10,11 In this communication, we report an
environmentally friendly synthetic methodology for
amination of aryl and (hetero)aryl compounds taking
place in DESs as reaction media. Working under air
and moderate heating and with no additional ligands,
the desired products are straightforwardly isolated in
up to 98% yield and with a broad substrate scope.
[1] Alonso, D.A; Baeza, A.; Chinchilla, R.; Guillena, G.; Pastor, I.M.; Ramòn, D.J.; Eur. J. Org. Chem., 2016, 612. [2] Smith, E.L.; Abbott, A.; Ryder, P.; Chem. Rev., 2014, 114, 11060. [3] Dilauro, G.; Quivelli, A.F.; Vitale, P.; Capriati, V.; Perna, F.M.; Angew. Chem. Int. Ed. Engl., 2019, 58, 1799. [4] Ghinato, S.; Dilauro, G.; Perna, F. M.; Capriati, V.; Blangetti, M.; and Prandi, C.; Chem. Commun., 2019, 55, 7741. [5] Dilauro, G.; Garcia, S.M.; Tagarelli, D.; Vitale, P.; Perna, F.M.; Capriati, V.; ChemSusChem., 2018, 11, 3495. [6] Garcìa-Àlvarez, J.; Eur. J. Inorg. Chem., 2015, 5147. [7] Garcìa-Alvarez, J.; Hevia, E.; Capriati, V.; Chem. Eur. J., 2018, 24, 14854. [8] Bhunia, S.; Pawar, G.G.; Kumar, S.V.; Jiang, Y.; Ma, D.; Angew. Chem. Int. Ed., 2017, 56, 16136. [9] Ma, D.; Cai, Q.; Zhang, H.; Org. Lett., 2003, 5, 2453. [10] Liu, S.; Zhou, J.; New J. Chem., 2013, 37, 2537. [11] Ferlin, F.; Trombettoni, V.; Luciani, L.; Fusi, S.; Piermatti, O.; Santoro, S.; Vaccaro, L.; Green Chem., 2018, 20, 1634. Acknowledgements: This work was financially supported by the Interuniversity Consortium C.I.N.M.P.I.S., by the University of Bari and has received funding by the European Union - PON FSE-FESR Ricerca e Innovazione 2014–2020, Azione I.1“Dottorati Innovativi con Caratterizzazione Industriale”.
POSTERS
61
Synthesis of Useful Aromatic Derivatives of Bile Acids Through Click Chemistry
(CuAAC)
Poster 35
V. Raglione,a* S. D’Auria,a B. Droghei,a A. Zerbini,a L. Romagnoli,a A. D’Annibale a
a Chemistry Department, La Sapienza University of Rome, Piazzale Aldo Moro 5, Roma, Italy, [email protected]
Bile acids 1 are a very important class of natural surfactants, showing themselves and their derivatives as
effective self-assembling materials (Figure 1). The morphology of bile acid derivative aggregates is strongly
dependent upon the substituents present both on the rigid steroid backbone and on the side chain, making them
suitable for applications in nanochemistry, sensing and drug delivery.1
In the last years, our group has been involved in a project concerning the preparation of bile acid derivatives,
bearing aromatic subunits on the C-3 of the steroid polycyclic ring.2 The Cu-promoted cycloaddition (click
reaction) of azides 2 to aromatic alkynes 3 was used as the key-step in the synthesis of such derivatives,
allowing us to synthesize bile acid-salicyl aldehyde derivatives 4, to be used as precursors of salophene
complexes, able to give self-assembly. The click chemistry approach was also useful to link the steroid
backbone to different aromatic subunits, such as ferrocene, allowing us to obtain compounds 5, able to
chemically modify the surface of carbon electrodes, for sensing applications (Figure 2).3
Figure 1. Bile acid structures.
Figure 2. Click chemistry in the preparation of aromatic BA derivatives.
[1] Nonappa, U. M., Org. Biomol. Chem. 2008, 6, 657. [2] Travaglini L., D’Annibale A., Di Gregorio M. C., Schillén K., Olsson U., Sennato S., Pavel N. V., Galantini L. J. Phys. Chem., 2013, 117, 9248-9257. [3] Rabti A., Raouafi N., Merkoçi A. Carbon, 2016, 108, 481–514.
POSTERS
62
Palladium Catalyzed Reductive Cyclization of Nitrobiphenyls Using Formate
Esters as CO Surrogates Poster 36
Doaa Reda Mohamed Ramadan,a* Francesco Ferretti,a Fabio Ragainia*
aDipartimento di Chimica, Università degli Studi di Milano, via Golgi 19, Milano, 20133, Italy [email protected]
Palladium complexes with phenanthroline ligands are so far the most effective catalysts for the reductive
cyclization of nitroarenes by carbon monoxide to yield a variety of heterocyclic compounds.[1] Despite the high
efficiency and the high atom-economical character of many of these reactions, they have not become of
widespread use. This is mainly attributed to the need for pressurized CO and pressure equipment (requiring CO
safety measures). In the aim of turning this kind of reaction into a “general tool” for the synthetic chemist, we
developed a procedure based on the use of phenyl formate as an in situ source of CO. The reaction can be
performed in a glass pressure tube, a cheap equipment accessible to every laboratory. Our previous work was
mainly focused on the synthesis of indoles by reductive cyclization of o-nitrostyrenes[2] and oxazines by the
hetero Diels-Alder condensation of a conjugated diene with a nitrosoarene formed in situ by the reduction of
the starting nitroarene.[3] However, the application of the previously developed method to the reductive
cyclization of 2-nitrobiphenyls to carbazoles (Scheme 1) afforded only moderate yields even under harsher
conditions and higher catalyst loadings. The result is not totally unexpected since this reductive cyclization is
known to be more difficult than the other previously studied. Here we report the results of our investigations
on this reaction aimed at both improving the catalytic performance and better understanding the reaction
mechanism.
Scheme 1. Reductive cyclization of 2-nitrobiphenyls to carbazoles using formates as CO source.
[1] a) F. Ferretti, D. Formenti, F. Ragaini, Rend. Fis. Acc. Lincei, 2017, 28, 97-115. b) F. Ragaini, S. Cenini, E. Gallo, A. Caselli, S. Fantauzzi, Curr. Org. Chem. 2006, 10, 1479-1510. [2] D. Formenti, F. Ferretti, F. Ragaini, ChemCatChem 2018, 10, 148-152. [3] M. A. EL-Atawy, D. Formenti, F. Ferretti, F. Ragaini, ChemCatChem 2018, 10, 4707-4717.
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63
Synthesis and Evaluation of Antimycobacterial Activity of Planar Chiral
Ferrocene Sulfonamides
Poster 37
Martin Ravutsov,a* Georgi Dobrikov,a Miroslav Dangalov,a Boris Shivachev,b
Violeta Valcheva,c Vladimir Dimitrova
a Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Science, Acad. G. Bonchev str. Bl. 9, 1113 Sofia, Bulgaria. b Institute of Mineralogy and Crystallography ‘‘Acad. Ivan Kostov’’, Bulgarian Academy of
Sciences, Acad. G. Bonchev str. Bl. 107, 1113 Sofia, Bulgaria. c Institute of Microbiology, Bulgarian Academy of Sciences, Acad. G. Bonchev str. Bl. 26, 1113 Sofia, Bulgaria.
Pulmonary tuberculosis (PTB) is among the two leading infectious causes of death worldwide.1 According
to World Health Organization (WHO) estimates, more than 9.0 million new cases and approx. 1.3 million
deaths occurred from PTB in 2017.1 The emergence of resistant strains limits the efficacy of existing drugs.
Thus, the current recommendations for PTB treatment involve a prolonged regimen of four to six drugs in
combination.1 Hence, the development of new drug candidates is essential to achieve the global TB targets set
in the Sustainable Development Goals and the End TB Strategy.1
Sulfonamdies were among the first effective drugs used to treat TB.2 Unfortunatelly, the development of
resistance through mutations in dihydropteroate synthase (DHPS) has limited their application.3 However, the
incorporation of other functionalities in addition to the sulfonamide group might be a suitable approach to
circumvent this issue.4 In this regard, herein, we report a synthetic approach for the preparation of new planar
chiral ferrocene sulfonamides (Figure 1) with potential anti-TB activity. Selected compounds were evaluated
for in vitro antibacterial activity against Mycobacterium tuberculosis H37Rv. The most active compounds were
studied against multi-resistant strains.
Figure 1.
[1] Global Tuberculosis Report 2018, World Health Organization. [2] Bentley, R. J. Ind. Microbiol. Biotechnol. 2009, 36, 775. [3] Yun, M.K., Wu, Y., Li, Z., Zhao, Y., Waddell, M.B., Ferreira, A.M., Lee, R.E., Bashford, D. and White, S.W. Science 2012, 335(6072), 1110. [4] de Souza, Marcus VN, Tuberculosis Treatment: The Search For New Drugs. Bentham Science Publishers: 2013.
POSTERS
64
Towars E-Selective Olefin Metathesis
Poster 38
Immanuel Reim,a*Giovanni Occhipinti,a Deryn. E. Fogg,b Vidar R. Jensena
a Department of Chemistry, University of Bergen, Allégaten 41, N-5007 Bergen, Norway. b Center for Catalysis Research & Innovation, and Department of Chemistry and Biomolecular Sciences, University of Ottawa, ON, Canada,
K1N 6N57. [email protected]
The formation of carbon-carbon bonds is the single most important reaction in organic chemistry.
Ruthenium-catalyzed olefin metathesis has attained great prominence as a potentially highly efficient
methodology for the assembly of both organic compounds (including active pharmaceutical ingredients, APIs),
and new materials. Recent frontier advances include Z-selective metathesis of terminal olefins. In contrast, the
challenge of E-selective metathesis remains unsolved.
Described herein are advances toward this goal using a state-of-the art approach integrating computational
prediction and experimental verification. Calculations indicate high selectivity for E-configured products via
thio-indole catalyst 1 (Figure 1): specifically, a high ∆∆G for the E- vs. the Z-selective transition states. The
synthesis and metathesis behavior of catalysts 1a–c will be discussed.
//
(a) (b)
Figure 1: (a) Structure of the thio-indole Ru complex. (b) X-ray crystal structure of the 7-thiol-2-phenyl-
indole derivative.
POSTERS
N
N
Mes
Mes
Ru N
S
R
R = H, Me, Ph 1a, 1b, 1c
65
The Stille Coupling to Synthesize b-Substituted Silver Corroles
Poster 39
Antonella Ricci,a* Manuela Stefanelli,b Marco Chiarini,a Claudio Lo Sterzo,a Roberto Paolesseb
a Facoltà di Bioscienze e Tecnologie Agro-Alimentari e Ambientali, Università degli Studi di Teramo, Via R. Balzarini 1, 64100 Teramo, Italy. b Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata”, Via della
Ricerca Scientifica 1, 00133 Roma, Italy. [email protected]
The palladium-catalyzed cross-coupling reaction of organostannanes with organic electrophiles, namely the
Stille reaction, is a very useful and versatile tool in the organic synthesis, due to its tolerance towards most
functional groups.1
In the last years, we have successfully explored,2 for the first time, the use of the Stille coupling in the
functionalization of corrole platforms,3 introducing alkynyl groups at the b-pyrrolic position.
In this report, we further explore the synthetic methodology by preparing a series of functionalized silver
complexes of corrole, with the aim to extend the corrole π-aromatic system and to modulate the electronic
delocalization by choosing electron-donating or electron withdrawing groups.
Figure 1. X-ray crystal structure of substituted corrole complex with R=H
[1] Farina, V.; Krishnamurthy, V.; Scott, W. J. The Stille Reaction, John Wiley & Sons, Inc., New York, 1998. [2] Stefanelli, M.; Naitana, M. L.; Chiarini, M.; Nardis, S.; Ricci, A.; Fronczek, F. R.; Lo Sterzo, C.; Smith, K. M.; Paolesse, R. Eur. J. Org. Chem. 2015, 6811-6816. [3] Nardis, S.; Mandoj, F.; Stefanelli, M.; Paolesse, R. Coord. Chem. Rev. 2019, 388, 360.
POSTERS
66
Gold(I)/Gold(III) Catalysis Merging Oxidative Addition and π-Alkene
Activation
Poster 40
M. Rigoulet,a* O. Thillaye Du Boullay,a A. Amgoune, a D. Bourissoua
a CNRS, Université Paul Sabatier, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA, UMR 5069),
Toulouse, France. [email protected]
Gold complexes are extremely powerful in activating π-bonds and the associated synthetic developments
are numerous. The faculty of hemilabile (P,N) ligands to promote the oxidative addition of aryl halides to gold,
as recently evidenced in our group,1 prompted us to try to combine oxidative addition and π-activation in a
Au(I)/Au(III)-catalysed transformation. In this respect, the oxy and amino-arylation reactions of alkenes with
aryl boronic acids and aryl diazonium salts represent very nice examples of gold redox catalysis under
oxidative2 and photoredox3 conditions, respectively.
Aiming at developing further Au(I)/Au(III) catalysis, we have developed a new gold-catalyzed
heteroarylation of olefins using the (MeDalphos)AuCl complex and found it efficiently promotes
these transformations from aryl iodides. This new reaction proceeds under mild conditions, works for
a large scope of substrates and does not require an external oxidant to generate the key gold(III)
intermediate. Catalytic results and associated mechanistic studies will be presented.
[1] a) A. Zeineddine, L. Estévez, S. Mallet-Ladeira, K. Miqueu, A. Amgoune, D. Bourissou, Nat. Commun. 2017, 8, 565; b) J. Rodriguez, A. Zeineddine, E. D. S. Carrizo, K. Miqueu, N. Saffon, A. Amgoune, D. Bourissou, Chem. Sci. 2019, DOI 10.1039/C9SC01954E. [2] G. Zhang, L. Cui, Y. Wang, L. Zhang, J. Am. Chem. Soc. 2010, 132, 1474. [3] B. Sahoo, M. N. Hopkinson, F. Glorius, J. Am. Chem. Soc. 2013, 135, 5505.
POSTERS
67
Development of a Dual Rh-P/Fe-C-Scorpionate Heterogeneous Catalysts for
Sequential Hydroformylation-Acetalization Reaction Poster 41
Fábio M. S. Rodrigues,a* Luísa M. D. R. S. Martins,b Mariette M. Pereira,a Armando J. L. Pombeirob
a Centro de Química de Coimbra, Departamento de Química, Universidade de Coimbra, Rua Larga, 3004-535 Coimbra, Portugal. b Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-
001 Lisboa, Portugal. [email protected]
Hydroformylation is one of the most important industrial transformations for olefin valorization. The
resulting aldehydes are often used as intermediates for several transformations both in bulk and fine chemistry.1
Due to this importance, several studies on sequential transformations under hydroformylation conditions have
been made in the last decades, which combine several steps in one single operation, increasing the sustainability
of the overall process.2,3 Particularly, the sequential reaction of aldehydes with alcohols affording acetal
products find several industrial applications.4
Envisioning an efficient one-step synthesis of acetals, starting from widely available and cheap olefins, in
this work, we present our studies on sequential hydroformylation-acetalization reactions, using
Rh(I)/P-Fe(II)/C-scorpionate dual catalytic systems. The synthesis and characterization of C-scorpionate
catalysts will be described and discussed. Additionally, we present our studies on the heterogenization of these
metal complexes on magnetic nanoparticles to obtain reusable catalysts.
Figure 1 Sequential approach for the direct synthesis of acetals from olefins via sequential hydroformylation-acetalization reaction. [1] Franke, R.; Selent, D.; Börner, A. Chem. Rev. 2012, 112, 5675. [2] Rodrigues, F. M. S.; Kucmierczyk, P. K.; Pineiro, M.; Jackstell, R.; Franke, R.; Pereira, M. M.; Beller, M.; ChemSusChem, 2018, 11, 2310. [3] Torres, G. M.; Frauenlob, R.; Franke R.; Börner, A. Catal. Sci. Technol., 2015, 5, 34. [4] Rodrigues, C.; Deloloa, F. G.; Norinder, J.; Börner, A.; Bogado, A. L.; Batista, A. A; J. Mol. Catal. A: Chem., 2017, 426, 586.
Acknowledgement: The authors thank Fundação para a Ciência e a Tecnologia (FCT) for the financial support to Coimbra Chemistry Centre (PEst-OE/QUI/UI0313/2014, PTDC/QEQ-MED/3521/2014), SunStorage project (POCI-01-0145-FEDER-016387) and to Centro de Química Estrutural (UID/QUI/00100/2019, PTDC/QEQ-ERQ/1648/2014 and PTDC/QEQ-QIN/3967/2014 projects). F. M. S. R. acknowledge the financial support from FCT (PD/BD/114340/2016 CATSUS PhD Program).
POSTERS
68
Ruthenium(II) Complexes with Alkoxysilylamino or Aminobis(phosphine)
Ligands. Synthesis, Characterization and Catalytic Activity towards Ethanol
Upgrading to Advanced Biofuels
Poster 42
Folasade J. Sama,a* Richard L. Wingad,a and Duncan F. Wassa
a School of Chemistry, Cardiff University, Park Place, Cardiff, CF10 3AT, UK.
Ruthenium(II) bis(phosphine) complexes have been explored by our group for ethanol and(or) methanol
upgrading to n-butanol/iso-butanol.1, 2 These isomers of butanol are termed “advanced biofuels” because their
fuel properties closely resemble those of gasoline.2 Here, we extend our studies to ruthenium complexes with
alkoxysilylamino (1), mono amine (2), or diamine (3) bis(phosphine) ligands. These bis(phosphine) complexes
containing one or two amine groups show remarkable activity towards ethanol upgrading. The presence of the
remote alkoxysilyl functional group in complex 1 offers a route for anchoring the catalyst onto support
materials. The synthesis of these materials, catalytic results and preliminary heterogenization experiments are
reported.
[1] G. R. M. Dowson, M. F. Haddow, J. Lee, R. L. Wingad and D. F. Wass, Angew. Chem. Int. Ed., 2013, 52, 9005-9008. [2] K. J. Pellow, R. L. Wingad and D. F. Wass, Catal. Sci. Technol., 2017, 7, 5128-5134.
POSTERS
69
Synthesis of Inherently Chiral 3,3’-Diheteroaryl-2,2’-Biindoles Using Suzuki-
Miyaura Cross-Coupling Reaction Poster 43
Luca Scapinello,a* Andrea Penoni,a Tiziana Benincori,a Federico Vavassori,a Gabriele Riva.a a Dipartimento di Scienza e Alta Tecnologia, Università degli Studi dell’Insubria, via Valleggio 9, 22100, Como – Italy
Inherently chiral materials based on 2,2’-biindole are characterized by an atropoisomeric backbone of two
2,2’ interconnected indole rings bearing 3,3’ substituents usually constituted by 2,2’bitiophene fragments or
their derivatives. Their principal application (as polymers obtained from enantiopure monomers) is in chiral
cyclic voltammetry as coating for working electrodes.1 Synthesis of those compounds shows as a key step a
Cacchi-Larock-type Pd-catalyzed cyclization starting from dialkyne 2 with two equivalents of heteroaryl
iodide as a coupling partner (Scheme 1).
Scheme 1
Since iodination is not accessible on all heterocycles, we developed a new synthetic pathway affording
biindoles exploiting classic Suzuki-Miyaura cross coupling reaction (Scheme 2). Further reactions will be
performed in order to expand 3,3’-diheteroaryl-2,2’biindoles and to explore their possible applications.
Scheme 2
[1] S. Arnaboldi, T. Benincori, A. Penoni, L. Vaghi, R. Cirilli, S. Abbate, G. Longhi, G. Mazzeo, S. Grecchi, M. Panigati, P.R. Mussini, Chem. Sci., 2019, 10, 2708.
POSTERS
70
Click-Functionalization of (dppf)Fe(CO)3 Poster 44
M. Schnierlea* and M.R. Ringenberga
a Universität Stuttgart, Institut für Anorganische Chemie, Pfaffenwaldring 55, 70550 Stuttgart. [email protected]
The compound, the (dppf)Fe(CO)3 molecule (dppf = 1,1'-bis(diphenyl-phosphino)ferrocene), on which the
presented work is based, was chosen because of its interesting properties. In preliminary work, this molecule
was synthesized and studied spectroelectrically, spectroelectrochemically and structurally. Some interesting
properties of the (dppf)Fe(CO)3 are the formation of a quasi iron-iron bond and a coordination change of the
ligands with the oxidation of the compound.[1]
The synthesis of the functionalized (dppf)Fe(CO)3 derivative is based on N,N-
dimethylaminomethylferrocene. The novel synthesized inter-mediates and complexes were analyzed
electrochemically and spectroscopically (IR, NMR, CV). Furthermore, it is to be determined how the geometric
and electronic structure of the system changes during the functionalization and immobilization.
[1] M. R. Ringenberg, F. Wittkamp, U.-P. Apfel, W. Kaim; Inorg. Chem., 2017, 56, 7501-7511.
POSTERS
71
Hydration of Alkynes Catalyzed by [(ppy)AuIII(NHC)X]X under Acid-Free
Conditions
Poster 45
Jacopo Segato,a* Alessandro Del Zotto,a Mattia Gatto,a Daniele Zuccaccia.a
a Dipartimento di Scienze Agroalimentari, Ambientali, e Animali, Sezione di Chimica, Università di Udine, Via Cotonificio 108, I-33100 Udine, Italy.
The hydration of alkynes is an important reaction in organic chemistry and is the one of the most
straightforward and environmentally friendly methods to form a carbon-oxygen bond.1 We have previously
reported on the chemistry and reactivity of Au(I) catalysts for this reaction in solvent, silver and acid free
conditions.2 or in green solvents.3 In this contribution, new Au(III) complexes of the type [(ppy)Au(NHC)X]
X (ppy= phenylpyridine; NHC = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, X- = BF4-, SbF6
-, OTf-)
were synthetized and tested as catalysts in the hydration of alkynes. A complete catalytic and kinetic
rationalization led us to develop a methodology under, silver-, and acid-free conditions working at mild (50
°C) temperature in neoteric solvent reducing the catalyst loading up to 1 mol % with respect to the substrate.
Figure 1
[1] Hintermann L.; Labonne A. Synthesis, 2007, 1121-1150. [2] Gatto M., Belanzoni P., Belpassi L., Biasiolo L., Del Zotto A., Tarantelli F.; Zuccaccia D. ACS Catal. 2016, 6, 7363−7376. Gatto, M.; Del Zotto, A.; Segato, J.; Zuccaccia, D. Organometallics 2018, 37, 4685−4691 [3] Gatto, M.; Baratta, W.; Belanzoni, P.; Belpassi, L.; Del Zotto, A. ; Tarantelli, F. ; Zuccaccia, D. Green Chem. 2018, 20, 2125-2134
POSTERS
3-hexyne
Water
3-hexanone
"# Silver "# Acid $% Mild Temperature $% Low catalyst loading $% Green solvent
72
Imidazolylidene Copper(II) Complexes: Synthesis and Re-Arrangement
Behaviour
Poster 46
Nathalie Ségaud,a* Jonathan McMaster,b Gerard van Koten,c and Martin Albrechta
a Departement of Chemistry & Biochemistry, Universität Bern, Freiestrasse 3, 3012 Bern, Switzerland. b School of
Chemistry, University of Nottingham, Nottingham, NG7 2RD, UK. c Organic Chemistry and Catalysis, Debye Institute for Materials Science, Faculty of Science, Utrecht University, 3584CG Utrecht, The Netherlands.
Copper enzymes are efficient catalysts for electron transfer and dioxygen activation. Histidine is
the common amino acid in the different active site types (Type 1, 2, 3 and CuA), and binds copper
through a well-established N-bonding mode. In synthetic complexes, C-bonding to different metal
centers has been observed by tautomerization processes. We are interested in inducing C-bonding
rather than N-bonding of an imidazole and in investigating its effect on the activity of selected copper
enzymes. For this purpose, N,N’-dimethylimidazolium-2-carboxylate (DMI-CO2) has been used as
an N-heterocyclic carbene (NHC) precursor. We successfully proved NHC-Cu(II) binding to a small
protein Type 1 modified active site, where redox processes where facilitated by a C-bonding mode.1
Here we will present the synthesis and spectroscopic characterisation of a series of unprecedented
copper(II) complexes with unsupported NHC ligands via a mild and general route and discuss specific
factors that govern distinct re-arrangement patterns of these complexes (Figure 1).2
Figure 1
Financial support by the H2020 MSCA-IF, ERC and SNF is gratefully acknowledged. [1] Planchestainer, M.; Segaud, N.; Shanmugam, M.; McMaster, J.; Paradisi, F.; Albrecht, M. Angew. Chem. Int. Ed. 2018, 57, 10677–10682. [2] Ségaud, N.; McMaster, J.; van Koten, G.; Albrecht, M. Manuscript in preparation.
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73
From Intra- to Intermolecular Policyclization of Dienynes Poster 47
Andrea Serafino,a Giovanni Maestria*
aDepartment SCVSA, University of Parma, Parco Area delle Scienze 17/A, 43124, Parma, Italy.
Photochemical reactions contribute in a significant way to the existing repertoire of carbon–carbon bond‐
forming reactions by allowing access to exceptional molecular structures that cannot be synthesized by
conventional means.1 This approach allows to obtain a wide range of polycyclic compounds from easily
accessible reagents. In a previous work a series of complex tetracyclic frameworks have been obtained from
the corresponding linear dienynes.2 The reaction enables the creation of four new carbon-carbon bonds and six
contiguous stereocenters. Currently ongoing developments focus on the extension of this intramolecular
reactivity to an intermolecular fashion.
[1] Chen, J.; Hu, X.; Lu, L.; Xiao, W.; Acc. Chem. Res., 2016, 49, 1911-1923. [2] Lanzi, M.; Santacroce, V.; Balestri, D.; Marchiò, L.; Bigi, F.; Maggi, R.; Malacria, M.; Maestri G.; Angew. Chem. Int., 2019, 58, 6703-6707
POSTERS
74
A Metal-Free Synthesis of N-Aryl Oxazolidin-2-ones by the One-Pot Reaction of
CO2 with N-Aryl Aziridines
Poster 48
M. Paolo Sonzini,a* Caterina Damiano,a Daniela Intrieri, a Emma Galloa
Department of Chemistry, University of Milan, via Golgi 19, 20133 Milano, Italy. [email protected]
Oxazolidinones are largely used as intermediates as well as chiral auxiliaries in organic synthesis1 and
constitute a class of active antibacterial and antibiotic compounds.2 The best pharmaceutical performances have
been usually observed for N-aryl oxazolidin-2-ones (NAOs), such as Linezolid,3Tedizolid4 and Toloxatone,5
which are FDA-approved drugs. One of the most interesting methodologies for the synthesis of NAOs is the
CO2 cycloaddition to aziridines, which employs this greenhouse gas as a renewable C1 synthetic building block.
Recently, we reported a ruthenium porphyrin-based catalytic procedure for synthesising N-alkyl oxazolidin-2-
ones6,7and, during our efforts to extend the same procedure to the synthesis of NAOs, we discovered that this
reaction was efficiently promoted by the very convenient TPPH2/TBACl catalytic system (TPPH2=tetraphenyl
porphyrin; TBACl=tetrabutyl ammonium chloride). Here, we report the optimization and study scope of the
synthesis of N-aryl oxazolidin-2-ones, which were obtained either by reacting CO2 with purified N-aryl
aziridines or by applying a two-steps procedure. The latter methodology consists in the Ru(TPP)CO-catalysed
synthesis of N-aryl aziridines that were converted into corresponding NAOs by the TPPH2/TBACl-catalysed
cycloaddition of CO2. By this pathway we obtained 20 different oxazolidinones with yields up to 99%,
moreover one of the synthesized products is an active Desaturase (D5D) Inhibitor.8
Figure 1: The two-step synthesis of NAOs
[1] Z. Vahideh and M. H. Majid, Curr. Org. Synth., 2018, 15, 3-20. [2] C. Roger, J. A. Roberts and L. Muller, Clin. Pharmacokinet., 2018, 57, 559-575. [3] A. Zahedi Bialvaei, M. Rahbar, M. Yousefi, M. Asgharzdeh and H. Samadi Kafil, J. Antimicrob. Chemoter., 2017, 72, 354-364. [4] D. McBride, T. Krekel, K. Hsueh and M. J. Durkin, Expert. Opin. Drug. Metab. Toxicol, 2017, 13, 331-337 [5] F. Moureau, J. Wouters, D. P. Vercauteren, S. Collin, G. Evrard, F. Durant, F. Durcey, J. J. Koenig and F. X. Jarreau, Eur. J. Med. Chem., 1992, 27, 939-948. [6] D. Carminati, E. Gallo, C. Damiano, A. Caselli and D. Intrieri, Eur. J. Inorg. Chem., 2018, 5258-5262. [7] D. Intrieri, C. Damiano, P. Sonzini and E. Gallo, J. Porphyrins Phtalocyanines, 2019, 23, 305-328. [8] Nobuyuki Matsunga et al., J. Med. Chem, 2017, 60, 8963-8981.
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75
Cobalt-Catalysed Suzuki Biaryl Cross-Coupling
Poster 49
Sanita Tailor,a* Mattia Manzotti,a Soneela Asghar,b Gavin Smith,c Robin Bedforda
a School of Chemistry, University of Bristol, Bristol, UK, BS8 1TS. b School of Life Sciences, University of Dundee,
Dundee, UK, DD1 5EH. c Heidelberg University, 69117 Heidelberg, Germany. [email protected]
Suzuki-Miyaura cross-coupling is a robust and widely exploited reaction used for the synthesis of new C-C
bonds, which when used in industry is usually catalysed by palladium. One of the targets for this area of
chemistry is to move away from the use of precious-metal catalysts to more sustainable alternatives. The use
of cobalt as a catalyst provides a possible solution to this due to its higher earth abundance and lower cost.
Herein we present one of few examples of cobalt-catalysed Suzuki biaryl coupling, and the only example to
show competence in using simple aryl chlorides and arylboronic esters as coupling partners (Figure 1).1-4
Figure 1: Cobalt-catalysed Suzuki cross-coupling of aryl chlorides and arylboronic esters
In this research we aim to work towards using milder conditions (through the use of alternative bases), and
to attain higher yields and better selectivity with lower catalytic loadings. Through mechanistic investigations,
such as kinetic studies, we have gained a greater understanding of how the reaction takes place, allowing for
further optimisation.
[1] Neely, J. M.; Bezdek, M. J.; Chirik, P. J. ASC Cent. Sci., 2016, 2, 12, 935. [2] Duong, H. A.; Wu, W.; Teo, Y-Y. Organomet., 2017, 36, 22, 4363. [3] Asghar, S.; Tailor, S. B.; Elorriaga, D.; Bedford, R. B.; Angew. Chem. Int. Ed., 2017, 56, 16367. [4] Tailor, S. B.; Manzotti, M.; Asghar, S.; Rowsell, B. J. S.; Luckham, S. L. J.; Sparkes, H. A.; Bedford, R. B. Organomet., 2019, 38, 8, 1770.
POSTERS
76
Pd@Ni-MOF Composites as Catalysts for Heck Arylation of Functionalized
Ofefins
Poster 50
Stanisława Tarnowicz-Ligus,a* Adam Augustyniak,a Anna M. Trzeciaka
a Faculty of Chemistry, University of Wroclaw, 14 F. Joliot-Curie, 50-383 Wroclaw, Poland.
Previous works over the Heck and Suzuki reactions using eugenol derivatives as substrates have been
described in paper.1 This promoted us to look for new materials containing both: palladium and phosphorus
ligand in their structure. We decided to test metal-organic frameworks (MOFs) as an organic support for two
palladium complexes of PdCl2P2.
In this work we would like to present our results of using the Pd@Ni-MOF composites as a catalyst in Heck
and Heck type reactions of eugenol and estragol (Figure 1). We have compared the influence of two palladium
complexes of PdCl2P2 type where P=tri(1-piperidinyl)phosphine (Pd-1) and triphenylphosphine (Pd-2)
immobilized on Ni-MOF material on yield and selectivity of these reactions. Both methods have generated
corresponding stilbenes (1 or 2). In the case of Heck type reaction product 1c was formed in subsequent catalytic
cycles with higher yields than product 1E/1Z. The reaction was studied with 0.5 - 1 mol% of palladium in DMF
as a solvent and using K2CO3 as a base in the Heck reaction or Cu(OAc)2 as an oxidative agent and was stirred
at 110 °C in oil bath. We have observed that in Heck arylation of estragol we obtained better results (76%
conversion) with immobilized Pd-1@Ni-MOF than with Pd-1 complex (67%). We have seen similar effect in
the case the immobilized Pd-2@Ni-MOF. However, when we carried out Heck type reactions using eugenol or
estragol with Pd@Ni-MOF composites we obtained lower yields of products than with Pd-1 or Pd-2 complex
only. In the further studies we have showed good results connected with the recycling of heterogenized Pd@Ni-
MOF catalyst.
Figure 1 Heck and Heck-type reactions of eugenole and estragol catalyzed by Pd@Ni-MOF
[1] Abdel Bar, F. M.; Khanfar, M. A.; Elnagar, A. Y.; Badria, F. A.; Zaghloul, A. M.; Ahmad, K. F.; Sylvester, P. W.; El Sayed, K. A. Bioorg. Med. Chem. 2010, 18, 496–507.
OH
O
O
eugenol
estragole
+
IOH
O
+OH
O
+
I
O+
O
base, DMF[Pd]
[Pd]base, DMF
1E/1Z 1b
2E/2Z 2b
B(OH)2[Pd]
Cu2+, DMF
B(OH)2
Cu2+, DMF
[Pd]
OH
O
O
O
+
1E/1Z 1c
POSTERS
77
Synthesis and Catalytic Application of Thiazolidines in Enantioselective
Reactions with Zinc Reagents
Poster 51
Nélia C. T. Tavares,a* Vanessa Cacho a, Dina Murtinho,a Elisa S. Serraa
a Chemistry Center and Department of Chemistry, University of Coimbra, Rua Larga 3004-535, Coimbra, Portugal
It is of general knowledge that chirality plays a central role in life related sciences, being the preparation of
optically active compounds a subject of major importance and constantly under research. Enantioselective
catalysis is one of the most effective methods to obtain these compounds, but, nevertheless, most of the
reactions require the use of toxic and expensive metals, such as rhodium, ruthenium, palladium and iridium.
The use of zinc species as catalysts is comparatively less developed and constitutes an interesting alternative
to these hazardous metals.1,2 The addition of diethylzinc or its derivatives to carbonyl compounds, under chiral
conditions, allows the formation of a new stereogenic center. Therefore, reactions such as enantioselective
alkylation and propargylation are of major interest, since they allow the preparation of optically active
secondary alcohols, versatile building blocks for the synthesis of a wide range of natural products and
pharmaceuticals.2,3 Several types of ligands can efficiently induce chirality in these reactions, highlighting
amino-alcohols as the most studied ones. Thiazolidines, heterocyclic compounds of sulfur and nitrogen, have
proven to act as good ligands for alkylation reactions, providing high ee.4 Since their application is practically
restricted to esterified derivatives, we set out to evaluate the catalytic efficiency of thiazolidine β-amino-alcohol
compounds as chiral ligands in this reaction (Figure 1). Taking advantage of these compounds and their ester
intermediates, we also prepared chiral progargylic alcohols with complete conversions and moderate ee. To the
best of our knowledge, this is the first example of the application of such ligands, with a simple synthetic
pathway, in enantioselective propargylation reactions.
Figure 1
[1] Soai, K. and Kawasaki, T. 2006. Enantioselective Addition of Organozinc Compounds. In: Rappoport, Z. and Marek, I.(eds). The Chemistry of Organozinc Compounds. John Wiley & Sons Ltd, West Sussex, pp.555-593. [2] Łowicki, D., Bas, S., Mlynarski, J. Tetrahedron 2015, 71, 1339. [3] Lu, G., Li, W-M., Li, X-S., Chan, A. S. C. Coordination Chemistry Reviews 2005, 249, 1736. [4] a) Serra, M. E. S.; Costa, D.; Murtinho, D.; Tavares, N. C. T.; Pinho e Melo, T. M. V. D. Tetrahedron 2016, 72, 5923. b) Tavares, N. C. T.; Neves, C. T.; Milne, B. F.; Murtinho, D.; Pais, A. A. C. C.; Serra, M. E. S. J. Organomet. Chem. 2018, 878, 1.
POSTERS
78
Studying the Influence of Fluorine Substituents on Rhodium-Amine Diolefin
Complexes
Poster 52
Esther Tschanen-Hammann,a* Hansjörg Grützmachera
a Department of Chemistry and Applied Biosciences, Federal Institute of Technology (ETH) Zürich, 8093 Zürich,
Switzerland. [email protected]
Transition metal amine diolefin complexes have been long studied in our group as catalysts for
dehydrogenation reactions of alcohols. One of the most efficient systems is the Rhodium-amine diolefin
complex (1) shown in Fig. 1. It has proven to be very efficient with a high TON of 106 when used as catalyst
for the Noyori-type dehydrogenation of ethanol under the formal loss of two equivalents of hydrogen gas (Eq.
1).1 However, the catalyst activation step requires the use of strong bases such as KOtBu. Furthermore, the
catalyst cannot liberate hydrogen gas and an acceptor, namely acetophenone, is required. The situation is quite
different when compared to Milstein’s work, where the Ruthenium catalysts release H2-gas at elevated
temperatures.2
Here we present the synthesis, structure, properties and the catalytic activity of the novel fluorine substituted
rhodium-amine diolefin complex (2). We have found that the acidity of the NH proton in (2) is two orders of
magnitude lower than in (1) with a pKa = 16.7±0.1. This enables the catalytic transformation of propane diol in
the presence of an amine base to the corresponding ammonium lactate (Eq. 2). As an amine base both DBU
(1,8-diazabicyclo[5.4.0]undec-7-ene) or TMG (1,1,3,3-tetramethylguanidine) can be used. The product lactate
can then be isolated as the ammonium salt by simple aqueous extraction. Previously, this transformation has
been reported only with the use of NaOH as base.3
[1] T. Zweifel, J.-V. Naubron, H. Grützmacher, Angewandte Chemie (International ed. in English) 2009, 48, 559. [2] C. Gunanathan, Y. Ben-David, D. Milstein, Science (New York, N.Y.) 2007, 317, 790. [3] M. Trincado, K. Kühlein, H. Grützmacher, Chem. Eur. J. 2011, 17, 11905.
POSTERS
Eq. 1: Catalytic dehydrogenation of ethanol to form ethyl acetate.1
Eq. 2: Catalytic dehydrogenative coupling reaction of propane diol to form lactates. As hydrogen acceptor, cyclohexanone or acetone can be used.3
Fig. 1: Structure of the Rhodium-amine diolefin complexes
R = H: See Ref. [1]; R = F: this work
79
The Rare Example of Stereoisomeric 2+2 Metallacycles of Porphyrins Featuring
Chiral Ruthenium Corners with C or A Handedness
Poster 53
A. Vidal,a* F. Battistin,a G. Balducci,a N. Demitri,b E. Iengo,a E. Alessioa
aDepartment of Chemical and Pharmaceutical Sciences, University of Trieste, Via L. Giorgieri 1, 34127 Trieste, Italy.
b Elettra - Synchrotron Light Source, S.S. 14 Km 163.5, Area Science Park, 34149 Basovizza, Trieste, Italy. [email protected]
We describe three new stereoisomers of the already known 2+2 metallacycle of porphyrins [trans,cis,cis-
RuCl2(CO)2(4′cisDPyP)]2 (1, 4′cisDPyP = 4′cis-dipyridylporphyrin), namely [{trans,cis,cis-
RuCl2(CO)2}(4′cisDPyP)2{cis,cis,cis-RuCl2(CO)2}] (2) and [cis,cis,cisRuCl2(CO)2(4′cisDPyP)]2 (3), in which
the chiral {cis,cis,cis-RuCl2(CO)2} fragment has either a C or A handedness.1 The least abundant 3 exists as a
mixture of two stereoisomers defined as alternate (3alt, both porphyrins are trans to a Cl and a CO) and
pairwise (3pw, one porphyrin is trans to two chlorides and the other to two carbonyls), each one as a statistical
mixture of meso (AC) and racemic (AA and CC) diastereomers. Remarkably, both 2 and 3 are – to the best of
our knowledge – unprecedented examples of 2D metallacycles in which the metal centers themselves are
chiral, and 2 is the first example of a 2+2 molecular square with stereoisomeric Ru(II) corners. Whereas 1 is
selectively obtained by treatment of trans,cis,cis-RuCl2(CO)2(dmso-O)2 (4) with 4′cisDPyP, 2 and 3 were
obtained, together with 1 (major product), using stereoisomers of 4, either cis,cis,trans-RuCl2(CO)2(dmso-S)2
or cis,cis,cis-RuCl2(CO)2(dmso)2, as precursors. From a general point of view, this work demonstrates that –
even for the smallest 2+2 metallacycle and using a symmetric organic linker – several stereoisomers can be
generated when using octahedral metal connectors of the type {MA2B2} that are not stereochemically rigid.
As a proof-of concept, it also opens the way to new – even though challenging – opportunities: unprecedented
and yet unexplored chiral metallo supramolecular assemblies can be obtained and eventually exploited (e.g.
for supramolecular catalysis) by using stereogenic metal connectors amenable to become chiral centers.
Figure 1. The meso and racemic forms of the metallacycles with the A and C chirality symbols on each corner, 3alt
metallacycles are omitted for the sake of clarity.
[1] Iengo, E.; Zangrando, E.; Minatel, R.; Alessio, E. J. Am. Chem. Soc. 2002, 124, 1003-1013.
POSTERS
80
Synergistic Catalysis upon Combination of Copper(II)-Triazapentadienate
Complexes and Carbon Nanotubes
Poster 54
Jiawei Wang,a Ana P. Ribeiro,a Marta S. Saraiva,b,c Maximilian N. Kopylovich,a Luísa M.D.R.S. Martinsa*
aCentro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal. bCentro
de Química e Bioquímica, DQB, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal. cBioISI -Biosystems & Integrative Sciences Institute, Departamento de Química e Bioquímica, Faculdade de
Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal. [email protected]
A synergistic catalysis, when overall performance of a catalytic system is much higher than individual
activity of its components, can significantly improve efficiency of many chemical processes. In this respect,
finding out combinations of catalytic species possessing remarkable synergetic action is of great interest.
Accordingly, In this presentation a new catalytic system for alcohol oxidation under microwave irradiation,
where copper(II)-triazapentadienate complexes are supported on carbon nanotubes (CNTs) is reported. These
synergetic catalysts lead to a 200 times higher overall activity compared to the complexes or CNTs taken alone,
and with TOFs reaching 1.9 x 104 h-1 (Figure 1). The reactional parameters, as well as the preparation procedure
will be discussed in this presentation.
Figure 1 a) Selective oxidation of alcohol to aldehyde catalyzed by 1@CNt and 2@CNT; b) The turnover
number for the oxidation of 1-phenylethanol catalyzed by complexes 1 or 2 in homogeneous or CNT-supported
conditions.
[1] Kopylovich, M.N.; Karabach, Y. Yu.; Guedes da Silva, M.F.C.; Figiel, P.J.; Lasri J.; Pombeiro, A.J.L. Chem. Eur. J. 2012, 18, 899-914. Acknowledgement: This research was supported by the Fundação para a Ciência e a Tecnologia (FCT), Portugal (UID/QUI/00100/2019, PTDC/QEQ-ERQ/1648/2014 and PTDC/QUI-QIN/29778/2017 projects) JW acknowledges FCT for the fellowship PD/BD/114397/2016. APC acknowledges the FCT and Instituto Superior Técnico (DL 57/2016 and L 57/2017 Program, contract IST-ID/119/2018). MSS thanks FCT for fellowship SFRH/BPD/88082/2012.
75119
1256415224
0
4000
8000
12000
16000
20000
0
100
200
300
400
500
1 2 1@CNT 2@CNT
TON
TON
POSTERS
a)
b)
81
Palladium Supported on Functionalized Polysiloxanes as a Reusable Catalyst for
the Heck Arylation of Homoallylic Substrates
Poster 55
Mattia A.Wirwis,a* U.Mizerska,b A.M. Trzeciak,a M.Cyprykb
a Faculty of Chemistry, University of Wroclaw, 14 F. Joliot – Curie St.,50-383 Wroclaw, Poland. bCentre of Molecular
and Macromolecular Studies, Polish Academy of Sciences, Engineering of Polymer Materials, 112 Sienkiewicza, 90-363 Lodz, Poland.
New and efficient heterogenized catalysts have become an increasingly attractive area of research in recent
times.1 A high stability under catalytic conditions, stabilization of the immobilized metal nanoparticles, almost
complete separation of the catalyst from the post-reaction mixture and its recycling are the most important
adavantages of this catalyst from the synthetical and industrial point of view.2 In the literature there are many
examples using of heterogenized catalysts, but particular attention should be paid to functionalized siloxane
polymers, which, despite low toxicity and high thermal and chemical resistance, are rarely used catalytic
carriers. Because of that in this paper we tried to show catalytic activity of imidazole (UM189) or pyridine
(UM202) functionalized polysiloxane which were impregnated by Pd(OAc)2 in synthesis of 4-aryl-2-butanones
and 4-aryl-3-buten-2-ones, widely used in the food and pharmaceutical industries; under the Heck reaction
conditions (Figure 1). In the case of 3-butene-2-one arylation, the reaction was carried out under microwave
conditions. After a one hour reaction at 120°C with 0.5 mol% Pd loading, 91% of 4-phenyl-3-buten-2-one were
obtained for Pd/UM189 and 83% of for Pd/UM202, respectively.After additional tests, it turned out that it is
possible to reduce the amount of palladium to 0.05mol% without any visible effect on the efficiency of the
reaction. Recycling carried out with both palladium-impregnated polysiloxanes showed a difference between
their catalytic activity. For the Pd/UM189 catalyst, about 20% reduction in the reaction yield was observed
after 7 catalytic cycles but for Pd/UM202 after four cycles. When the substrate was changed to unsaturated
alcohol - 3-buten-2-ol, the reaction was carried out for 6 hours using oil bath heating according to the procedure
which was developed for the homogeneous catalyst earlier. However, for the heterogenized polysiloxanes
proposed here, it was necessary to increase the temperature from 90oC to 120oC. An increase in yield of 4-
phenyl-2-butanone was observed and finally 89% for Pd/UM189 and 70% for Pd/UM202 was optained. In case
of this substrate also difference in catalytic activity
during the recycling process was observed. Only in the
case of an imidazole-functionalized polysiloxane
(Pd/UM189), a 11 subsequent catalytic cycles were
carried out with the around 90% yield of 4-phenyl-2-
butanone.
Figure 1 Synthesis of 4-aryl-2-butanones and 4-aryl-3-buten-2-ones under the Heck reaction conditions. [1] Polshettiwar V.; Len C.; Fihri A. Coord. Chem. Rev. 2009, 253, 2599. [2] Mieczyńska E.; Borkowski T.; Cypryk M.;Pośpiech P. Appl.Catal. A: General 2014, 470, 24.
POSTERS
82
C–H Bond Arylations of 1,2,3-Triazoles by Reusable Pd/C Catalyst in Solvent-
Free Conditions
Poster 56
F. N. Zappimbulso,a* A. Punzi,a G. M. Farinolaa
aDepartment of Chemistry, University of Bari, Via Orabona 4, 70010 Bari, Italy. [email protected]
The 1,2,3-triazole ring represents a key structural motif in various applied areas, such as drug discovery,1
bioconjugation,2 and materials science.3 Among the known methods for the regioselective synthesis of fully
substituted 1,2,3-triazoles, the Pd-catalyzed direct arylation of the easy available 1,4-disubstituted 1,2,3-
triazoles turns out to be the most general approach.4 The major drawback of this synthetic methodology is still
represented by the use of toxic solvents. Only few examples of direct arylation protocols of 1,4-disubstituted
1,2,3-triazoles based on the use of more sustainable conditions have been reported in the literature. For
example, protocols for Pd-catalyzed direct arylations in environmentally-benign reaction media, such as
polyethylene glycol (PEG) 5 or biomass-derived g-valerolactone, in the presence of reusable palladium
catalysts, were developed by Ackermann and coworkers. In the frame of our studies on triazole-based
materials6 as well as on Pd-catalyzed reactions for the synthesis of heteroaromatic compounds,7 we report here
in the first Pd-catalyzed direct arylation protocol of 1,4-disubstituted 1,2,3-triazoles that is performed in (i)
solvent-free, (ii) non-anhydrous conditions, (iii) without exclusion of air, and (iv) in the presence of a reusable
catalyst (Figure 1). Then, with the aim of making the reaction conditions more sustainable, we evaluated the
possibility of using only tetra-n-
butylammonium acetate (Bu4NOAc) as the
base and the reaction medium, in the absence
any other additive. Using Pd/C (5 mol %) as the
catalyst, we examined the role of the halogen,
reaction temperature and catalyst loading. To probe catalyst reusability, we recovered the Pd/C by a modified
literature protocol and evaluated the catalytic activity of the recycled material in the subsequent run. We
observed an unchanged catalytic activity of the recycled Pd/C until the third run, while a halving of its activity
is detected at the fourth run. Having selected Pd/C (5 mol %) in the presence of neat Bu4NOAc as the best
reaction system, we investigate the substrate versatility reacting the 1,2,3-triazoles, having a different ring
substitution pattern, with various aryl iodides. [1] a) E. Bonandi, M. S. Christodoulou, G. Fumagalli, D. Perdicchia, G. Rastelli, D. Passarella, Drug Discov. Today, 2017, 22, 1572-1581; b) D. Dheer, V. Singh, R. Shankar Bioorg. Chem. 2017, 71, 30-54. [2] C. J. Pickens, S. N. Johnson, M. M. Pressnall, C. J. Berkland, Bioconjugate Chem. 2018, 29, 686-701. [3] a) J. E. Moses, A. D. Moorhouse Chem. Soc. Rev. 2007, 36, 1249-1262; b) J-F. Lutz, Angew. Chem. Int. Ed. 2007, 46, 1018-1025. [4] C. Zhang, L. You, C. Chen Molecules 2016, 21, 1268. [5] X. Tian, F. Yang, M. Bauer, S. Warratz, L. Vaccaro, L. Ackermann Chem. Commun., 2016, 52, 9777-9780. [6] A. Punzi, A. Ardizzone, N. Ventosa, I. Ratera, J. Veciana, G. M. Farinola Eur. J. Org. Chem. 2016, 15, 2617-2627 [7] a) A. Punzi, N. Zappimbulso, G. M. Farinola Monatshefte für Chemie-Chemical Monthly, 2019, 150, 59-66; b) A. Punzi, S. Di Noja, R. Ragni, N. Zappimbulso, G. M. Farinola J. Org. Chem. 2018, 83, 9312-9321.
POSTERS
Figure 1
83
Fluorescent organic dyes for Luminescent Solar Concentrators
Poster 57
Costanza Papucci,a,b* Massimo Calamante,b Lorenzo Zani,b Greta Santi,c Giuseppe Iasilli,c Andrea Pucci,c Gianna Reginatob and Alessandro Mordinib
a Department of Biotechnologhy, Chemistry and Pharmacy University of Siena, Via A. Moro 2, 53100, (SI) Italy. b ICCOM-CNR Via Madonna del Piano 10, 50019, (FI) Italy. c Department of Chemistry and Industrial Chemistry
Univesrity of Pisa, Via A.G. Moruzzi 13, 56124, (PI) Italy. [email protected]
Luminescent Solar Concentrators (LSCs) are photovoltaic device of third generation, composed by a
polymer doped with a dye, in contact with a PV cell. The aim of the device is to improve the photovoltaic
efficiency of the PV cell, reducing the costs of materials and of installations1. The design of fluorophore is a
crucial step. In this work we foculized our attention on benzo-bisthiazole core and quinoxaline one. New
organic dyes were synthetized and characterized spectroscopically in solution and in different polymer
matrices. The best results are achieved for quinoxaline derivatives showing a good optical efficiency, about
10%, higher than the commercial reference, Lumogen Red 305 (η=7.4%) at the same concentration (1.8% w/w).
Figure 1
[1] Papucci, C.; Geervliet, T. A.; Franchi, D.; Bettucci, O.; Mordini, A.; Reginato, G.; Picchioni, F.; Pucci, A.; Calamante, M. and Zani, L. Eur. J. Org. Chem., 20, (2018), 2657-2666.
POSTERS
84
Robust Organo-Diiron Complexes as Potential Anticancer Agents
Poster 58
S. Schoch,a* G. Agonigi,a L.K. Batchelor,b L. Biancalana,b T. Biver,a S. Braccini,a F. Chiellini,a P.J. Dyson,b T. Funaioli,a F. Marchetti,a G. Pampaloni,a S. Zacchinic
a Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Moruzzi 13, Pisa, Italy. b Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland. c Dipartimento di
Chimica Industriale “Toso Montanari”, Università di Bologna, Viale Risorgimento 4, Bologna, Italy. [email protected]
Diiron cationic complexes containing a bridging vinyliminium ligand are available by a gram-scale
procedure from the commercial Fe2Cp2(CO)4, via stepwise assembly of isocyanide, methyl and alkyne
moieties. The synthetic pathway (see scheme below) is general and has been used to prepare a broad range of
complexes with different R and R’ substituents and, consequently, different chemical and physico-chemical
properties.
The cationic vinyliminium complexes are susceptible to nucleophilic attack due to their net positive charge.
Thus, diiron nitrile-amino-allylidene complexes can be obtained via regio-selective addition of cyanide (from
NBu4CN) to the Cα carbon of the bridging ligand (see scheme below). This is a feasible strategy to accomplish
clean and facile C-C bond formation.
Despite deriving from classical organometallic synthesis, all products are stable upon air/water contact and
the parent vinyliminium compounds also display acceptable water solubility (up to 9 g/L). The antiproliferative
activity towards A2780 and A2780cisR cancer cell lines and non-tumorigenic HEK-293 cells has been
assessed for selected compounds. The IC50 values indicate that the cytotoxic activity and cancer cell selectivity
can be tuned by varying the nature of R and R' substituents. In order to elucidate the mechanism of action,
various studies have been carried out, including electrochemical analysis, ROS assessment and interaction with
model biomolecules.
Further reading
[1] Marchetti; Eur. J. Inorg. Chem., 2018, 3987-4003, and references therein. [2] A. G. Agonigi, M. Bortoluzzi, F. Marchetti, G. Pampaloni, S. Zacchini, V. Zanotti; Eur. J. Inorg. Chem., 2018, 960-971.
POSTERS
85
Reactivity of Silane compounds with few-layer black phosphorus
Poster 59
Inigo Iglesias,a* Andrea Ienco,a Maria Caporali,a Martina Banchelli,b Paolo Matteini,b Manuel Serrano-Ruiz,a Maurizio Peruzzinia
a CNR-ICCOM, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy. b CNR-IFAC, Via Madonna del Piano 10,
50019 Sesto Fiorentino, Italy. [email protected]
2D materials have attracted the interest of researchers around the world due to their outstanding properties
and potential applications in many fields such as optoelectronics and sensing. Among those 2D materials,
phosphorene, which consists on a single layer of bulk orthorhombic black phosphorus1, seems to be promising.
Yet, the instability of this material in air and its tendency to degrade very quickly via reaction with oxygen and
water is a major drawback that impedes its direct application.2 Therefore, for the last years, research efforts
have been devoted to the chemical functionalization of this fascinating nanomaterial in order to improve its
stability.3 It is known that SiO2 coating is a common process that has been previously used in many
nanomaterials, such as carbon nanotubes.4 This kind of coating does not alter its electronic structure
significantly and improving their resistance to degradation. In this work, we have studied the reactivity of few-
layers black phosphorus with various silane compounds such as TEOS and PDMS. Characterization of the
reaction products (IR, Raman, TEM, etc.) shows the layers of BP are containing silicon compounds and that
the flakes are free of SiO2 nanoparticles on its surface. Analysis via EDX confirmed the presence of Si whose
quantity depends on the reaction conditions.
Further reading
[1] Materials Chemistry and Physics 2017, 189, 215-229. [2] 2D Mater. 2018, 5, 032001. [3] Adv. Mater. 2018, 30, 1704749. [4] Nano Letters 2002, 2, 329. Acknowledgements: Thanks are expressed to the European Research Council (ERC) for funding the project PHOSFUN “Phosphorene functionalization: a new platform for advanced multifunctional materials” (Grant Agreement No. 670173) through an ERC Advanced Grant to M. P. and to the University of Siena.
POSTERS
86
Surname Name Lecture Page
Ackermann Lutz 3 15 Manuel Alcarazo 12 24 Olivier Baudoin 9 21 Angela Casini 7 19 Gallo Emma 2 14
J. A. Gareth Williams 5 17 Anny Jutand 11 23
Jerome Lacour 8 20 Maria Conception Gimeno 4 16
Lukas Gooßen 10 22 Eduardo Peris 13 25 Nguyen Bao N. 1 13 Maurizio Taddei 14 26
Simon Woodward 6 18
INDEX OF LECTURERS
87
Surname Name Poster Page
Annunziata Alfonso 1 27 Bagnarelli Luca 2 28 Baldino Salvatore 3 29 Baratta Walter 3 29
Bartalucci Niccolò 4 30 Bazzi Sokna 5 31 Berti Beatrice 6 32
Bösken Jonas 7 33 Brambilla Elisa 8 34 Caligiuri Rossella 9 35 Cataffo Andrea 10 36
Chiurchiù Elena Chuanpan Guo Colombo Gioele 11 37
Dabrowska Anna M 12 38 Dell'Aera Marzia 13 39
Dentoni Litta Antonella 14 40 Esposito Roberto 15 41
Farre Perez Albert 16 42 Fenghe Duan Franchi Daniele 17 43
Fusi Giovanni Maria 18 44 Gahlot Sweta Gatto Giordano 19 45
Gentili Dario Ghinato Simone 20 46
Gianangeli Matteo 21 47 Gomes Carla 22 48 Guarra Federica 23 49 Iglesias Iñigo 59 85
Impemba Salvatore 24 50 Jurt Pascal 25 51
Kusio Jaroslaw Leone Ezio
Librando Ivy 26 52 Longhi Andrea 27 53 Luciani Lorenzo 28 54
Manzotti Mattia 49 75 Melchiorre Massimo 15 41 Menichetti Stefano
Navazio Federica Nylund Pamela 29 55 Paolini Edoardo Papucci Costanza 57 83 Pastore Genny
Pelliccioli Valentina 30 56 Piccirillo Giusi 31 57 Pirovano Valentina 32 58
INDEX OF PARTICIPANTS
88
Proietti Giampiero 33 59 Quivelli Andrea Francesca 34 60 Ragaini Fabio 36 62 Raglione Venanzo 35 61 Ramadan Doaa Reda Mohamed 36 62 Ravutsov Martin 37 63 Reginato Gianna
Reim Immanuel 38 64 Ricci Antonella 39 65
Rigoulet Mathilde 40 66 Ringenberg Mark Rodrigues Fabio 41 67
Ruffo Francesco 1 27 Sama Folasade Josephine 42 68
Saponaro Simone Scapinello Luca 43 69 Schnierle Marc 44 70 Schoch Silvia 58 84 Segato Iacopo 45 71 Ségaud Nathalie 46 72 Serafino Andrea 47 73
Sirignano Marco Sonzini Paolo 48 74
Staffolani Antunes Steeples Elliot Tailor Sanita 49 75
Tarnowicz-Ligus Stanislawa 50 76 Tavares Nelia 51 77
Tschanen-Hammann Esther 52 78 Vallesi Riccardo
Vanden Broeck Sofie Vidal Alessio 53 79 Wang Jiawei 54 80
Wirwis Anna 55 81 Yuan Lixia
Zappimbulso Nicola 56 82
INDEX OF PARTICIPANTS
89
Sunday, 1 September: start 16.00
Surname Name Number Time
Alfonso Annunziata 1 16:00 Niccolò Bartalucci 2 16:04 Sokna Bazzi 3 16:08
Beatrice Berti 4 16:12 Elisa Brambilla 5 16:16
Gioele Colombo 6 16:20 Anna Maria Dabrowska 7 16:24
Marzia Dell'Aera 8 16:28 Roberto Esposito 9 16:32 Daniele Franchi 10 16:36 Carla Gomes 11 16:40
Federica Guarra 12 16:44 Lorenzo Luciani 13 16:48 Pamela Nylund 14 16:52
INDEX OF FLASH PRESENTATIONS
90
Monday, 2 September: start 17.30
Surname Name Number Time
Andrea Cataffo 1 17:30 Costanza Papucci 2 17:34 Valentina Pelliccioli 3 17:38
Giusi Piccirillo 4 17:42 Giampiero Proietti 5 17:46
Andrea Francesca Quivelli 6 17:50 Doaa Reda Mohamed Ramadan 7 17:54
Immanuel Reim 8 17:58 Antonella Ricci 9 18:02 Mathilde Rigoulet 10 18:06
Fábio Rodrigues 11 18:10 Folasade Josephine Sama 12 18:14
Jacopo Segato 13 18:18 Nathalie Ségaud 14 18:22 Sanita Tailor 15 18:26 Matteo Giannangeli 16 18:30 Mark Schnierle 17 18:34
INDEX OF FLASH PRESENTATIONS