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12th Congress of the Interdivisional
Group of Organometallic Chemistry
Hotel Bristol Palace
Genoa, June 5–8, 2016
Organized by
Dipartimento di Chimica e Chimica Industriale, Università di Genova
ABSTRACT BOOK
2
List of Contents
Sponsorship 3
Organization 4
Welcome 5
Scientific Programme 6
Plenary Lectures 11
Keynote Lectures 18
Oral Communications 25
Posters 51
List of Participants 83
List of Authors 87
3
UNDER THE AUSPICES OF
SPONSORS
4
ORGANIZATION
Chairperson
Renata Riva
Scientific Committee
Roberto Ballini (Presidente Divisione Chimica Organica)
Silvia Bordoni (G.I.C.O.)
Pier Giorgio Cozzi (G.I.C.O.)
Antonella Dalla Cort (Past-Coordinatore G.I.C.O.)
Carlo Nervi (G.I.C.O.)
Fabio Ragaini (Coordinatore G.I.C.O.)
Gianna Reginato (G.I.C.O.)
Renata Riva (G.I.C.O.)
Adriana Saccone (Presidente Divisione Chimica Inorganica)
Local Organizing Committee
Renata Riva (chairperson)
Giorgio Cevasco (Presidente Sezione Liguria)
Simona Delsante
Massimo Maccagno
Lisa Moni
Adriana Saccone (Presidente Divisione Chimica Inorganica)
Organizing Secretariat
c/o Dipartimento di Chimica e Chimica Industriale Università degli Studi di Genova,
Via Dodecaneso 31, 16146 Genova, e-mail: [email protected], phone: +39
010 3536126.
5
Welcome to Co.G.I.C.O. 2016
Welcome to the XII Congress of the Interdivisional Group of Organometallic
Chemistry (Co.G.I.C.O.) of the Italian Chemical Society, which will take place in
Genoa in the period June 5–8, 2016. The Conference will be held at the Bristol Palace
Hotel, in via XX Settembre, placed in the heart of the city.
The congress has reached its twelfth edition demonstrating the great interest of
inorganic and organic chemists for organometallic chemistry. This is also confirmed
by the fact that the G.I.C.O., with its c.a. 130 participants, is the largest
interdivisional group of the SCI.
Over the years, the scientific interest addressed by many researchers, with
different backgrounds, to the chemistry of organometal compounds and their
potential application in many fields, has promoted the development of
interdisciplinary fields of research such as bioorganometallic chemistry and
materials science, focused on nanotechnologies, as well as on new materials and
processes whose goal is to produce zero-carbon energy. The researchers working in
the field of organometallic chemistry have paid particular attention to sustainable
processes, as witnessed by the continuing evolution of catalytic reactions. Recent
examples are the development of gold chemistry, the pairing of metallic catalysts
with organic catalysts to allow reactions otherwise not possible.
Moreover, the potential applications derived from the knowledge gained from
studies of organometallics are evolving, promising significant progress in that field.
The G.I.C.O. congress is a biennial event and represents a possibility for
researchers working in this field to spread their results and share new ideas. These
can promote the creation of new partnerships, giving a great benefit for the cultural
growth of the entire chemical community.
Renata Riva
Co.G.I.C.O Chairperson
6
SCIENTIFIC PROGRAMME
Hotel Bristol Palace, Genova
Sunday, 5th June
12.50 – 15.30 Registration
15.30 – 16.00 Opening
Chairman: Roberto Gobetto
16.00 – 16.50 PL1 Maurizio Peruzzini – CNR-ICCOM, Sesto Fiorentino
"White, Red and Black: playing with phosphorus allotropes from
organometallic chemistry to innovative 2D-materials"
16.50 – 17.10 OC1 Emanuela Licandro: Università di Milano
"Metal-mediated reactions for the heteroaryl-heteroaryl bond
formation: non photochemical synthesis of thiahelicenes
17.10 – 17.40 KN1 Francesca Cadorna – Università di Firenze
"Carbohydrate derived compounds and their reactions with metals
and organometals en route to the synthesis of nitrogen containing
heterocycles"
17.40 – 18.00 OC2 Valentina Fiorini – Università di Bologna
"Ir(III) and Re(I) tetrazolate-based luminescent complexes. Ion pairs,
heterometallic dyads and sensing abilities"
18.00 – 18.20 OC3 Carlo Nervi – Università di Torino
"Chemically modified electrode surfaces for CO2 reduction"
18.20 – 18.30 Valentina Cinti – CiaoTech, Milano
"CIAOTECH PNO partner in REE4EU, Indus3Es and MEMERE
projects"
19.00 – 20.30 Welcome Reception
7
Monday, 6th June
Chairman: Luca Banfi
9.00 – 9.50 PL2 Thomas J. J. Müller – Heinrich Heine Universität, Düsseldorf
"Sequentially Pd- and Pd-Cu-catalyzed one-pot syntheses of
functional heterocycles"
9.50 – 10.10 OC4 Roberto Gobetto – Università di Torino
"Electrocatalytic CO2 reduction by Mn(bpy-R)(CO)3Br complexes"
10.10 – 10.30 OC5 Monica Dell'Acqua – Università di Milano
"MediaChrom: exploring a new family of pyrimidoindolone-based
polarity-sensitive dyes"
10.30 – 11.00 Coffee Break
Chairman: Silvia Bordoni
11.00 – 11.30 KN2 Riccardo Pettinari – Università di Camerino
"The development of anticancer drugs based on half-sandwich
organometallic complexes containing bidentate donor ligands"
11.30 – 11.50 OC6 Andrea Penoni – Università dell'Insubria
"Synthesis of 3,3'-substituted-2,2'-biindoles and 2,2'-substituted-3,3'-
biindoles: high valuable compounds for material science"
11.50 – 12.10 OC7 Valerio Zanotti – Università di Bologna
"Bond forming reactions involving isocyanides mediated by diiron
complexes"
12.10 – 12.30 OC8 Alessio Dessì – CNR-ICCOM, Sesto Fiorentino
"Pd-catalysed synthesis of blue organic dyes and their application as
sensitizers for near-IR absorbing dye-sensitized solar cells"
12.30 – 12.50 OC9 Marco Baron – Università di Padova
"Recent developments on gold(III) complexes with di(N-heterocyclic
carbene) ligands"
12.50 – 15.00 Lunch Break
15.00 – 16.00 Poster Session (P1-P14)
Chairman: Gianna Reginato
16.00 – 16.30 KN3 Cristiano Zuccaccia – Università di Perugia
8
"Investigating the activation and transformation of catalysts for olefin
polymerization and water oxidation by NMR"
16.30 – 16.50 OC10 Chiara Lambruschini – Università di Genova
"Design and synthesis of multifunctional fluorescent magnetic
nanoparticles for promising biomedical applications"
16.50 – 17.20 Coffee Break
Chairman: Valeria Conte
17.20 – 18.10 PL3 Enrico Marcantoni – Università di Camerino (GICO Senior
Award)
"The cerium-carbon bond in useful organometallic reagents for the
synthesis of biologically relevant small molecules"
18.10 – 18.30 OC11 Chiara Capacci – Università di Bologna
"New nickel-phosphorus homoleptic carbonyl clusters: synthesis,
characterization, and catalytic properties"
18.30 – 20.30 Assemblea GICO
Tuesday, 7th June
Chairman: Maurizio Peruzzini
9.00 – 9.50 PL4 Gabriele Manca – CNR-ICCOM, Sesto Fiorentino (Bonati
Award)
"Electron transfers in organometallic chemistry and catalysis:
integrated computational/experimental studies"
9.50 – 10.10 OC12 Claudio Pettinari – Università di Camerino
"Pyrazole-based ligands: a useful tool for bioinorganic,
organometallic and material chemistry"
10.10 – 10.30 OC13 Alissa C. Götzinger – Heinrich Heine Universität, Düsseldorf
"Rapid one-pot synthesis of heterocycles by sequentially palladium-
catalysed one-pot processes"
10.30 – 11.00 Coffee Break
Chairman: Enrico Marcantoni
11.00 – 11.30 KN4 Ioannis Houpis – Janssen-API Development, Beerse
9
"Diverse olefin synthesis via permutations of the Barluenga reaction"
11.30 – 11.50 OC14 Umberto Piarulli – Università dell'Insubria
"Supramolecular interactions for highly selective transition-metal
catalysis"
11.50 – 12.10 OC15 Roberto Esposito – Università di Napoli Federico II
"Highly conjugated blue dimers of platinum(II)"
12.10 – 12.30 OC16 Valeria Conte – Università di Roma Tor Vergata
"Ferrocenylporphyrins: from synthesis to photoelectrochemical
dioxygen activation"
12.30 – 12.50 OC17 Alessandro Caselli – Università di Milano
"Silver(I) catalyzed Henry reaction"
12.50 – 15.00 Lunch Break
15.00 – 16.00 Poster Session (P15-P29)
Chairman: Vito Capriati
16.00 – 16.30 KN5 Antonio Papagni – Università di Milano-Bicocca
"Cross-coupling reaction-based synthesis of organic semiconductors:
non always an easy way"
16.30 – 16.50 OC18 Daniela Intrieri – Università di Milano
"'Totem' C2-symmetrical iron(III) porphyrin complexes to
stereoselectively promote alkene cyclopropanation"
16.50 – 17.20 Coffee Break
Chairman: Carlo Nervi
17.20 – 18.10 PL5 Marc Robert – Université Paris Diderot
"Molecular catalysis of the reduction of CO2 with iron porphyrins.
From mechanistic studies to optimization of catalysts and to efficient
electrolizers for CO2 splitting into CO and O2
18.10 – 18.30 OC19 Manuel Anselmo – Università di Genova
"Highly convergent synthesis of intensively blue emissive furo[2,3-
c]isoquinolines by a palladium-catalyzed cyclization cascade of
unsaturated Ugi products"
20.00 Social Dinner at the cloister of the Cathedral of Genova
10
Wednesday, 8th June
Chairman: Valerio Zanotti
9.00 – 9.30 KN6 Barbara Milani – Università di Trieste
"Iminopyridines: versatile ligands for palladium catalyzed
polymerization reactions"
9.30 – 9.50 OC20 Stefano Brenna – Università dell'Insubria
"σ-Donor and π-acceptor properties of substituted phenanthroline
ligands in [Mo(CO)4(phen*)] complexes: an ETS-NOCV analysis"
9.50 – 10.10 OC21 Luca Mengozzi – Università di Bologna
"Iron complexes as effective photocatalysts for the asymmetric
alkylation of aldehydes"
10.10– 10.30 OC22 Gabriel Menendez Rodriguez – Università di Perugia
"Positional effect of a hydroxyl group on the activity of pyridyl-
carboxylate catalysts for water oxidation"
10.30 – 11.00 Coffee Break
Chairman: Emanuela Licandro
11.00 – 11.20 OC23 Alessandro Cimino – Università dell'Insubria
"Catalytic properties of pyrazolato-based metal-organic frameworks
with exposed metal sites"
11.20 – 11.40 OC24 Dario Formenti – Università di Milano
"Reductive cyclization of nitro compounds using CO surrogates:
formate esters at work"
11.40 – 12.30 PL6 Vito Capriati – Università di Bari Aldo Moro
"Reshaping the future of polar organometallic chemistry toward
sustainability: new challenges, strategies, and tactics with
organolithium compounds"
12.30 – 12.50 Poster Prize
12.50 – 13.00 Closing Ceremony
11
PLENARY LECTURES
PL1
12
White, Red and Black: playing with phosphorus allotropes from
organometallic chemistry to innovative 2D-materials
Maurizio Peruzzini
CNR-ICCOM, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy, email:
The lecture will provide an overview of the most recent achievements in the area of
transition metal-mediated reactivity of elemental phosphorus deriving from the
authors' own research in Florence. Highlights will include:
the activation of white phosphorus with particular emphasis to the unusual hydrolytic
behavior of the P4 molecule following its η1-coordination to a metal centre (Fe, Ru,
Os), which affords a variety of organometallic compounds stabilizing unusual low-
valent phosphorus species as ligands [1];
the high pressure reactivity of red phosphorus towards water and other small
molecules [2];
our preliminary results in exploring the chemistry of the less reactive allotrope of the
element, i.e. black phosphorus [3], including the easy access to 2D-flakes of
phosphorene (the all-P counterpart of graphene) via a solution synthesis which
avoids the use of boring and scarcely productive scotch-tape exfoliation procedures
and its reactivity with organometallic synthons.
Figure 1. The different allotropes of phosphorus exhibit different reactivity
Acknowledgments: MP thanks all the coworkers listed in the references. Thanks are expressed to EC through the SUSPHOS grant RFP7-PEOPLE-2012-ITN - 317404 and to the European Research
Council for funding the project PHOSFUN "Phosphorene functionalization: a new platform for
advanced multifunctional materials”(GA No. 670173) through an ERC Advanced Grant).
[1] Barbaro, P.; Bazzicalupi, C.; Peruzzini, M.; Seniori Costantini, S.; Stoppioni P. Angew. Chem.
Int. Ed. 2012, 51, 8628 and references therein.
[2] Ceppatelli, M.; Bini, R.; Caporali, M.; Peruzzini, M. Angew. Chem. Int. Ed. 2013, 52, 2313. [3] Serrano-Ruiz, M.; Caporali, M.; Ienco, A.; Piazza, V.; Heun, S.; Peruzzini, M. Adv. Mater.
Interfaces 2015, 2, 1400225.
PL2
13
Sequentially Pd- and Pd-Cu-catalyzed one-pot syntheses of
functional heterocycles
Thomas J. J. Müller
Institut für Organische Chemie und Makromolekulare Chemie, Heinrich Heine
Universität Düsseldorf, Universitätstr. 1, D-40225 Düsseldorf, Germany, email:
Multi-component and domino reactions are efficient and effective methods in the
rapid and diversity-oriented synthesis of heterocycles. In particular, transition metal
catalyzed multi-component sequences have recently gained a considerable interest
[1]. Based upon the Pd-catalyzed entry to ynones, diynones, and enones and
sequentially Pd-catalyzed processes [2] we have opened new avenues to one-pot
syntheses of numerous classes of heterocyclic frameworks [4]. Most interestingly, in
sequentially Pd-catalyzed processes the same catalyst source is operative a second
time without further catalyst addition. This one-pot methodological concept is most
elegantly applied to the syntheses of halochromic luminescent pyranoindoles, and to
very concise syntheses of marine alkaloids and kinase inhibitors, also by applying a
general Masuda-borylation-Suzuki-arylation sequence to the synthesis of bridged
bisindoles.
[1] D’Souza, D. M.; Müller, T. J. J. Chem. Soc. Rev. 2007, 36, 1095.
[2] a) Merkul, E.; Dohe, J.; Gers, C.; Rominger, F.; Müller, T. J. J. Angew. Chem. Int. Ed. 2011,
50, 2966. b) Müller, T. J. J. Top. Heterocycl. Chem. 2010, 25, 25. c) Müller, T. J. J. Synthesis
2012, 44, 159.
[3] a) Müller, T. J. J. Top. Organomet. Chem. 2006, 19, 149. b) Lessing, T.; Müller, T. J. J. Appl.
Sci. 2015, 5, 1803.
[4] a) Willy, B.; Müller, T. J. J. Curr. Org. Chem. 2009, 13, 1777. b) Müller, T. J. J. Top. Heterocycl. Chem. 2010, 25, 25. c) Müller, T. J. J. Synthesis 2012, 44, 159. d) Gers-Panther,
C. F.; Müller, T. J. J. Adv. Heterocycl. Chem. 2016, manuscript accepted.
PL3
14
The cerium-carbon bond in useful organometallic reagents for the
synthesis of biologically relevant small molecules
Enrico Marcantoni
School of Science and Technology, Chemistry Division, University of Camerino,
Via S. Agostino 1, 62032 Camerino, Italy, email: [email protected]
The rare earth metal compounds come to play a significant role in synthesis, because
the majority of rare earth metal catalysts show characteristic properties of sustainable
catalysts, such as low cost, aqueous/air/thermal stability, recyclability, and last but
not the least high catalytic efficiency [1]. Among the lanthanides cerium deserves
particular attention due to the widely use in organic chemistry [2]. The Ce3+ ion is a hard cation in according to HSAB theory of Pearson, and shows a strong
affinity towards hard bases such as oxygen and nitrogen donor ligands. However, in these
last years, the improvement of the properties of organocerium species has allowed to reveal how these organometallic reagents to be synthetically useful allowing the formation of new
C-C bonds [3]. The organocerium compounds have gained considerable importance not only
in organometallic chemistry, and have had a marked relevance in the synthesis of complex
molecules. Several small molecules of interest for the discovery of potential drugs can thus be prepared
by efficient synthetic procedures that use specie containing carbon-cerium bonds.
[1] Kobayashi, S. Lanthanides: Chemistry and Use in Organic Synthesis; Springer: Berlin, 1999.
[2] Bartoli, G.; Marcantoni, E.; Marcolini, M.; Sambri, L. Chem. Rev. 2010, 110, 6104.
[3] Marcantoni, E.; Sambri, L. In Comprehensive Organic Synthesis, 2nd edition, Vol. 1; Molander,
G. A.; Knochel, P. Eds.; Elsevier: Oxford, 2014, pp 267.
NO
NH
O
S
O
O CH3
OH OH
NH
OOHO N
NH
O
O
O
OH
Me
HN
O
NMe2
OO
O
O
Me
O
OH
HO
PL4
15
Electron transfers in organometallic chemistry and catalysis:
integrated computational/experimental studies
Gabriele Manca1, Carlo Mealli1, Andrea Ienco1, Emma Gallo2, Maurizio Peruzzini1
1 CNR-ICCOM, via Madonna del Piano 10, 50019 Sesto Fiorentino(FI), Italy,
email: [email protected] 2 Dipartimento di Chimica, Università di Milano, Via Golgi19, 20133 Milano, Italy
Electron transfer processes are ubiquitous and appealing when involving a transition
metal. These events are fast and hard to monitor experimentally, but the modern
computational methods highlight the milestones in possible reaction pathways also
correlating stereochemistry, electronic structure and energy costs.
With DFT calculations, different Ru complexes have been investigated, since able to
activate organic azides, phosphine oxides and diiodine, respectively. The processes
are relevant in the fields of catalysis, tautomerization and the dynamic evolution of
halogen-bonded systems.
Initially, comparable Ru-porphyrin complexes will be discussed for their roles in
amination and aziridination catalysis involving azides. After the N2 departure, a
“NR” group (uncharged or in the imido form) remains linked to the metal. The
theoretical analysis indicated that the nitrene ligand, as a diradical, can activate a
C-H linkage of some organic substrate, leading to different nitrogen products, in
catalytic fashion. In particular, two interconnected cycles were foreshadowed, both
involving the so called “rebound mechanism”. In anyone, the N-H and N-C bonds
would form in a sequence. The theoretically envisaged reaction mechanisms were
also corroborated by ad-hoc experiments [1].
Another case study highlights the Ru role in the H3POH2POH tautomerization, in
which H transfer is not of the acid-base type but implies electron transfer through the
metal, while in its absence H3PO is unreactive [2].
Finally, the reaction between [Ru(CNtBu)4Cl2] and I2 was investigated, due to the
thermodynamically disfavored substitution of the Cl- with the I- ligands to give the
1D solid state product {[Ru(CNtBu)4Cl2]*I2}n. The theoretical-experimental study
indicates its stepwise formation through in-situ formed mixed trihalide. Eventually,
I-Cl separates from the I-coordinated ClI2- ligand. The process is endergonic, hence
facilitated by higher temperatures [3].
[1] a) Manca, G.; Gallo, E.; Intrieri, D.; Mealli, C. ACS Catal. 2014, 4, 823. b) Zardi, P.; Pozzoli,
A.; Ferretti, F.; Manca, G.; Mealli, C.; Gallo, E. Dalton Trans. 2015, 44, 10479. c) Manca, G.;
Mealli, C.; Carminati, D. M.; Intrieri, D.; Gallo, E. Eur. J. Inorg. Chem. 2015, 4885.
[2] Manca, G.; Caporali, M.; Ienco, A.; Peruzzini, M.; Mealli, C. J. Organomet. Chem. 2014, 760,
177.
[3] Mosquera, M. E. G.; Gomez-Sal, P.; Diaz, I.; Aguirre, L. M.; Ienco, A.; Manca, G.; Mealli, C.
Inorg. Chem. 2016, 55, 283.
PL5
16
Molecular catalysis of the reduction of CO2 with iron porphyrins.
from mechanistic studies to optimization of catalysts and to
efficient electrolizers for CO2 splitting into CO and O2
Marc Robert
Université Paris Diderot, Sorbonne Paris Cité, Laboratoire Electrochimie
Moléculaire, UMR CNRS 7591, 15 rue Jean de Baïf, 75013 Paris, France, email:
Recent attention aroused by the reduction of carbon dioxide has as main objective
the production of useful products the “solar fuels” in which solar energy would
be stored. One route to this goal consists in first converting sunlight energy into
electricity than could be further used to reduce CO2 electrochemically. Conversion
of carbon dioxide into carbon monoxide is a key-step through the classical
dihydrogen-reductive Fischer-Tropsch chemistry. We will describe our work in this
field using various iron tetraphenylporphyrin derivatives, that prove to be remarkable
catalysts of the reduction of CO2 to CO when generated electrochemically at the
Fe(0) oxidation state, both in terms of selectivity, durability, overpotential and
turnover frequency [1-6]. Understanding the molecular mechanisms for catalysis
allows identifying the main factors that control the process and optimizing the
catalyst structure [7].
Extending these studies, we recently discovered that it was possible, with a water-
soluble Fe porphyrin, to catalyze the electrochemical conversion of carbon dioxide
into carbon monoxide in pure water [8] as well as to transfer catalytic activity to solid
surfaces by grafting of the molecular catalysts [9]. Finally, and based on these
advances, we very recently designed an efficient electrolyzer for CO2 splitting in
neutral water using only earth abundant materials [10].
[1] Drouet, S.; Costentin, C.; Robert, M.; Savéant, J-M. Science, 2012, 338, 90.
[2] Costentin, C.; Robert, M.; Savéant, J-M. Chem. Soc. Rev. 2013, 42, 2423.
[3] Costentin, C.; Passard, G.; Robert, M.; Savéant, J-M. a) J. Am. Chem. Soc. 2013, 135,
9023. b) J. Am. Chem. Soc. 2014, 136, 11821.
[4] Costentin, C.; Robert, M.; Savéant, J-M. Acc. Chem. Res. 2015, 48, 2996.
[5] Costentin, C.; Passard, G.; Robert, M.; Savéant, J-M. PNAS, 2014, 111, 14990. [6] Bonin, J.; Robert, M.; Routier, M. J. Am. Chem. Soc. 2014, 136, 16768.
[7] Robert M. et al. submitted.
[8] Costentin, C.; Robert, M.; Savéant, J-M.; Tatin, A. PNAS, 2015, 112, 6882.
[9] Maurin, A.; Robert, M. J. Am. Chem. Soc. 2016, 138, 2492.
[10] Robert M. et al. PNAS 2016, in press.
PL6
17
Reshaping the future of polar organometallic chemistry toward
sustainability: new challenges, strategies, and tactics with
organolithium compounds
Vito Capriati
Università degli Studi di Bari “Aldo Moro”, Dipartimento di Farmacia–Scienze
del Farmaco, Consorzio C.I.N.M.P.I.S., Via E. Orabona 4, I-70125 Bari, Italy,
email: [email protected]
The environmental impact associated with chemical synthesis has recently posed
severe and compelling demands for sustainable chemistry, and the development of
cost-effective and environmentally benign reaction systems in place of volatile and
harsh organic compounds represents an active field of research. Polar organometallic
chemistry has become a cornerstone of modern organic synthesis, however, with an
heavy impact on the environment [1]. The burgeoning field of oxygen heterocycles
has also seen significant breakthroughs over the last ten years particularly because
of the blossoming of new lithiation methodologies for the preparation of more
functionalised derivatives in which the solvent proved to play a central role in
mediating the degree of aggregation, and thus the reactivity of the corresponding
organolithium compounds. Contributions from this laboratory to the development of
such lithiation strategies will be revealed [2]. In addition, this lecture will discuss the
potential benefits of using environmentally friendly, bio-based “deep eutectic
solvents” (DESs), low melting mixtures (LMMs) based on carbohydrates/urea,
[3a,b] and more challengingly also water [3c] as effective, unconventional reaction
media for s-block-metal-mediated organic transformations run at room temperature
and under air.
[1] García-Álvarez, J.; Hevia, E.; Capriati, V. Eur. J. Org. Chem. 2015, 6779.
[2] a) Coppi, D. I.; Salomone, A.; Perna, F. M.; Capriati, V. Chem. Comm. 2011, 47, 9918; b)
Coppi, D. I.; Salomone, A.; Perna, F. M.; Capriati, V. Angew. Chem. Int. Ed. 2012, 51, 7532;
c) Mansueto, R.; Mallardo, V.; Perna, F. M.; Salomone, A.; Capriati, V. Chem. Comm. 2013,
49, 10160; d) Mansueto, R.; Perna, F. M.; Salomone, A.; Florio, S.; Capriati, V. Chem. Comm.
2013, 49, 4911; e) Salomone, A.; Perna, F. M.; Falcicchio, A.; Nilsson Lill, S. O.; Moliterni,
A.; Michel, R.; Florio, S.; Stalke, D.; Capriati, V. Chem. Sci. 2014, 5, 528; f) Cicco, C.;
Addante, V.; Temperini, A.; Donau, C.; Karaghiosoff, K.; Perna, F. M.; Capriati, V. Eur. J.
Org. Chem. 2016, DOI: 10.1002/ejoc.2001600365.
[3] a) Mallardo, V.; Rizzi, R.; Sassone, F. C.; Mansueto, R.; Perna, F. M.; Salomone, A.; Capriati, V. Chem. Comm. 2014, 50, 8655; b) Sassone, F. C.; Perna, F. M.; Salomone, A.; Florio, S.;
Capriati, V. Chem. Comm. 2015, 51, 9459; c) Cicco, L.; Sblendorio, S.; Mansueto, R.; Perna,
F. M.; Salomone, A.; Florio, S.; Capriati, V. Chem. Sci. 2016, 7, 1992.
18
KEYNOTE LECTURES
KN1
19
Carbohydrate derived compounds and their reactions with metals
and organometals en route to the synthesis of nitrogen containing
heterocycles
Francesca Cardona
Università di Firenze, Dipartimento di Chimica “Ugo Schiff”, Via della Lastruccia
3-13, 50019, Sesto Fiorentino (FI), Italy, email: [email protected]
Carbohydrates are an excellent and cheap source of multiple stereogenic centers with
a well-defined configuration, often employed in the chiral pool strategy to afford
enantiopure target compounds. In turn, metals and organometallic reagents are able
to undergo selective reactions in order to promote the stereoselective formation of
new stereocenters. The combination of these two chemical tools opens the way to
the synthesis of nitrogen-containing heterocycles, in particular to glycomimetics of
particular biological and therapeutic relevance, such as iminosugars [1] and
aminosugars [2].
We report herein how the reactions of carbohydrate-derived aldehydes and nitrones
could be employed in reactions with organometal derivatives to synthesize new
polyhydroxylated alkaloids of biological interest [3]. Moreover, the application of
the osmium-catalyzed tethered aminohydroxylation (TA) reaction [4] on
carbohydrate derivatives such as glycals and glycals-derived compounds allowed the
synthesis of new aminosugars [5].
[1] Compain P.; Martin, O. R. in Iminosugars: from Synthesis to Therapeutic Applications, Eds.;
Wiley VCH, New York, 2007.
[2] a) Dwek, R. A. Chem. Rev. 1996, 96, 683; b) Sánchez-Fernández, E. M.; García Fernández, J.
M.; Ortiz Mellet, C. Chem. Commun. 2016, 52, 5497.
[3] a) Cardona, F.; Moreno, G.; Guarna, F.; Vogel, P.; Schuetz, C.; Merino, P.; Goti. A. J. Org.
Chem. 2005, 70, 6552; b) Parmeggiani, C.; Cardona, F.; Giusti, L.; Reissig, H.-U.; Goti A.
Chem. Eur. J. 2013, 19, 10595; c) Parmeggiani, C.; Catarzi, S.; Matassini, C.; D’Adamio, G.;
Morrone, A.; Goti, A.; Paoli, P.; Cardona, F. ChemBioChem 2015, 16, 2054. [4] Donohoe, T. J.; Callens, C. K. A.; Lacy, A. R.; Winter C. Eur. J. Org. Chem. 2012, 655.
[5] Mirabella, S.; Cardona, F.; Goti, A. Org. Lett. 2015, 17, 728.
KN2
20
The development of anticancer drugs based on half-sandwich
organometallic complexes containing bidentate donor ligands
Riccardo Pettinari, Fabio Marchetti, Claudio Pettinari
University of Camerino, via S. Agostino 1, 62032 Camerino, Italy, email:
In the search for anticancer agents containing metals other than platinum, ruthenium
compounds have become promising alternatives to platinum-based drugs [1].
I will discuss our work on the design of potential anticancer half-sandwich
organometallic RuII, RhIII and IrIII complexes containing curcuminoid ligands
obtained from the rhizome of Curcuma longa [2].
Curcumin (1,7-bis-(4-hydroxy-3-
methoxyphenyl)-1,6-heptadiene-3,5-dione) is
the major component of turmeric, with the
characteristic yellow color, well-known for its
traditional medicinal properties. The
therapeutic values include anti-inflammatory,
antioxidant, antibacterial, antiviral, antifungal
and anticancer activity and more than 65
clinical trials have been carried out on this
substance. However, the major problem
involving curcumin is its poor bioavailability leading to low levels in plasma and
tissues [3].
The reports from our group have shown that curcumin in the metal bound form
retains, and in some cases increases, its therapeutic potential. We have studied the
structure-activity relationships for these half-sandwich complexes with different
curcuminoids, counterions, ancillary ligands and metals. We have shown that some
complexes containing curcumin-based ligands as potential leaving groups are not
only endowed with superior solubility properties, but also superior selectively and
cytotoxicity with respect to cisplatin toward some human cancer cells.
[1] Nazarov, A. A.; Hartinger, C. G.; Dyson, P. J. J. Organomet. Chem. 2014, 751, 251.
[2] a) Pettinari, R.; Marchetti, F.; Pettinari, C.; Condello, F.; Petrini, A.; Scopelliti, R.; Riedel, T.;
Dyson, P.J. Dalton Trans. 2015, 44, 20523; b) Pettinari, R.; Marchetti, F.; Condello, F.;
Pettinari, C.; Lupidi, G.; Scopelliti, R.; Mukhopadhyay, R.; Riedel, T.; Dyson, P.J.
Organometallics, 2014, 33, 3709; c) Caruso, F.; Rossi, M.; Benson, A.; Opazo, C.; Freedman,
D.; Monti, E.; Gariboldi, M.B.; Shaulky, J.; Marchetti, F.; Pettinari, R.; Pettinari, C. J. Med. Chem. 2012, 55, 1072.
[3] a) Prasad, S.; Gupta, S. C.; Tyagi, A. K.; Aggarwal, B.B. Biotechnol. Adv. 2014, 32, 1053–
1064; (b) Wanninger, S.; Lorenz, V.; Subhan, A.; Edelmann, F. T. Chem. Soc. Rev. 2015, 44,
4986.
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21
Investigating the activation and transformation of catalysts for
olefin polymerization and water oxidation by NMR
Cristiano Zuccaccia
Department of Chemistry, Biology and Biotechnology and CIRCC, University of
Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy, email:
The comprehension of catalyst structure-reactivity relationships is a fundamental
step toward a rational optimization of homogeneous transition metal catalysts.
However, "catalytic recipes" frequently include the use of additives (activators,
scavengers, etc...) in addition to (pre)catalyst(s) and substrates. Dissecting and
understanding the various reactive/unreactive interactions between all these
components, which play a pivotal role in determining the overall activity and
selectivity of the catalysts, is thus of primary importance to rationalize the overall
catalytic performances. Thanks to the high content of detailed information at the
molecular level, NMR spectroscopy is one of the leading spectroscopic techniques
to directly face this problem. Combining several information from multinuclear and
multidimensional experiments, NMR methods can be successfully exploited to
precisely determining the molecular and/or supramolecular structure in solution of
pre-catalysts, catalytic active species, (off-loop) intermediates and/or species
deriving from catalyst transformation or deactivation.
In this communication, the application of 1D and 2D NMR methodologies in the
fields of transition metal catalyzed olefin polymerization and water oxidation will be
illustrated using selected examples. In a first example, the role of an unusual M-CAryl
bond in determining activation and self-modification of pyridyl-amido olefin
polymerization catalysts will be discussed [1]. In a second example, it will be shown
how the interaction of [Cp*IrL1L2L3]Xn water oxidation catalysts with sacrificial
oxidants, such as cerium ammonium nitrate, sodium periodate or hydrogen peroxide,
determines the progressive oxidative transformation of the catalyst [2] and how this
transformation is modulated by the nature of ancillary ligands (L) and experimental
conditions.
[1] a) Zuccaccia, C.; Macchioni, A.; Busico, V.; Cipullo, R.; Talarico, G.; Alfano, F.; Boone, H.
W.; Frazier, K. A.; Hustad, P. D.; Stevens, J. C.; Vosejpka, P. C.; Abboud, K. A. J. Am. Chem.
Soc. 2008, 130, 10354; b) Zuccaccia, C.; Busico, V.; Cipullo, R.; Talarico, G.; Froese, R. D.
J.; Vosejpka, P. C.; Hustad, P. D.; Macchioni, A. Organometallics 2009, 28, 5445.
[2] Zuccaccia, C.; Bellachioma, G.; Bortolini, O.; Bucci, A.; Savini, A.; Macchioni, A. Chem.-
Eur. J. 2014, 20, 3446.
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22
Diverse olefin synthesis via permutations of the Barluenga reaction
Ioannis N. Houpis
Janssen-API Development, Small Molecules, Beerse, Belgium, email:
In this talk I will discuss the initial synthesis development of a key intermediate of
an API, using the Barluenga reaction.
During that work, several observations allowed us to realize that the reaction could
be suitably modified to allow for a concise synthesis of various olefinic derivatives
by simple internal “collapse” of aryl sulfonyl hydrazones depending on the
electronics of the aryl group. In the case of severely electron deficient substrates, the
failure of the internal “collapse” can be turned into an advantage by utilizing external
sulfonate salts as nucleophiles.
KN5
23
Cross-Coupling reaction-based synthesis of organic
semiconductors: non always an easy way
Antonio Papagni
Department of Materials Science, University of Milano-Bicocca, 20125 Milano,
Italy, email: [email protected]
The cross-coupling reaction represents an important tool in organic synthesis which
allows the preparation of a large number organic systems by metal catalysed C-C
bond formation starting from organo metallic and organohalide precursors. The
reaction is of general applicability since suitable experimental condition combined
with right metal catalysts makes it compatible with a wide variety of organic
functionalities.
For these peculiar features the Cross-coupling reaction is the elective protocol for a
straightforward preparation of molecular or polymeric organic semiconductors with
potential application in soft electronic, in electroluminescent and photovoltaic
systems. Despite this general applicability, the nature of starting materials and their
reactivity sometime drives the reaction towards a different pathway affording
unexpected products. In this presentation the results obtained in the synthesis of p
and n-type organic semiconductors belong to oligothiophene [1], tetracene [2,3] and
polyfluorophenazine families are presented. In the synthesis of these systems the
cross coupling reaction represents the key step and the unexpected results obtained
applying the standard conditions reported in the literature for similar substrates has
forced to individuate suitable modifications in order to overcome the encountered
problems.
[1] a) Papagni, A. et al. J. Am. Chem. Soc. 2006, 128, 13378; b) Papagni, A. et al. Synthetic Metals
2004, 145, 7; c) Papagni, A. et al. J. Mater. Chem. 2004, 14, 171.
[2] Papagni, A. et al. Eur. J. Org. Chem. 2011, 4160.
[3] Papagni, A. et al. Organometallics 2011, 30, 4325.
KN6
24
Iminopyridines: versatile ligands for palladium catalyzed
polymerization reactions
Barbara Milani
Department of Chemical and Pharmaceutical Sciences, University of Trieste, Via
Licio Giorgieri 1, 34127 Trieste, Italy, email: [email protected]
Thanks to their cheap, relatively easy and modular synthesis, iminopyridines are
widely used as ancillary ligands in coordination chemistry. Their relevant iron,
cobalt, nickel and palladium complexes have been applied as homogeneous catalysts
for alkene oligomerization and homopolymerization [1].
In this lecture I will highlight the results we have recently obtained on the use of
iminopyridines as ancillary ligands for both mononuclear and dinuclear
palladium(II) complexes.
The collection of ligands and complexes we investigated allowed to point out some
common features in their characterization both in solid state and in solution, such as
the effect of methyl groups of the ligand on the Pd-CH3 fragment 1H NMR chemical
shift and the presence of cis and trans isomers. The complexes were tested as
precatalysts for both the CO/vinyl arene and the ethylene/methyl acrylate
copolymerization reactions.
As a case history of the mononuclear derivatives, the unprecedented comonomer
dependence of the stereochemistry control in the palladium catalyzed CO/vinyl arene
polyketone synthesis will be discussed [2]. Whereas for the dinuclear complexes, the
catalytic behavior in the ethylene/methyl acrylate copolymerization will be
presented.
[1] a) Boudier, A.; Breuil, P.-A. R.; Magna, L.; Olivier-Boubigou, H.; Braunstein, P. Chem.
Commun. 2014, 50, 1398; b) Bianchini, C.; Mantovani, G.; Meli, A.; Migliacci, F.; Laschi, F.
Organometallics 2003, 22, 2545.
[2] Canil, G.; Rosar, V.; Dalla Marta, S.; Bronco, S.; Fini, F.; Carfagna, C.; Durand, J.; Milani, B.
ChemCatChem 2015, 7, 2255.
25
ORAL COMMUNICATIONS
OC1
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Metal-mediated reactions for the heteroaryl-heteroaryl bond
formation: non photochemical synthesis of thiahelicenes
Emanuela Licandro, Silvia Cauteruccio, Davide Dova
Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi 19, 20133
Milano, Italy, email: [email protected]
Tetrathia[7]helicenes (7-TH), are chiral helical-shaped polyaromatic systems
containing four thiophene and three benzene rings. They exhibit peculiar electronic
and chiroptical properties suitable for applications in optoelectronics [1], biology [2],
and catalysis [3]. For these reasons they are emerging as one of the most popular
class of chiral helical-shaped molecules. We are deeply involved in the development
of these molecules, with a particular focus on innovative synthesis of the helical
scaffold through metal-mediated cross-coupling reactions.
In this presentation, our recent studies on the synthesis of 7-TH derivatives using
cross-coupling reactions at different stages of the synthetic sequence will be
illustrated. The most recent results are reported in the scheme below.
[1] 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.
[2] Cauteruccio, S.; Bartoli, C.; Carrara, C.; Dova, D.; Errico, C.; Ciampi, G.; Dinucci, D.;
Licandro, E.; Chiellini, F. Chem. Plus. Chem. 2015, 80, 490.
[3] Cauteruccio, S.; Dova, D.; Benaglia, M.; Genoni, A.; Orlandi, M.; Licandro, E. Eur. J. Org.
Chem. 2014, 2694.
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Ir(III) and Re(I) tetrazolate-based luminescent complexes. Ion
pairs, heterometallic dyads and sensing abilities
Valentina Fiorini1, Stefano Stagni1, Massimiliano Massi2
1 Department of Industrial Chemistry “Toso Montanari”, University of Bologna
Viale Risorgimento 4, 40136 Bologna, Italy, email: [email protected] 2 Department of Chemistry, Curtin University, WA 6102 Bentley, Australia.
The spotlight of our research program is the preparation and the study of the physical
and chemical properties of transition metal complexes containing 5-aryl tetrazolate
[R-CN4]- moiety. In particular we have demonstrated how these synthetically
versatile nitrogen-rich ligands can actually rule the photophysical behavior of the
corresponding Ru(II), Ir(III), Re(I) and Pt(II) – based species [1,2]. The synthetic
versatility of tetrazolate derivatives combined with the peculiar sensitivity to
electrophiles that is displayed by the metal-coordinated tetrazolate group constitute
the background for the further development of their coordination chemistry and their
applicative fields. With a similar pathway, we have prepared a the first examples of
anionic Ir(III) tetrazolate complexes and new Re(I)-based species containing ditopic
tetrazolate ligands [3,4]. (Figure 1) The photophysical properties of the new
molecules, with particular attention dedicated to their use as components both for
luminescent ion pairs and covalently linked dyads, together with the study of their
chemosensing abilities, will be discussed.
[1] Stagni S. et al. Inorg. Chem. 2014, 53, 229.
[2] Stagni S. et al. Dalton Trans. 2015, 44, 8379.
[3] Fiorini V. et al. Dalton Trans. 2015, 44, 20597.
[4] Fiorini V. et al. Dalton Trans. 2016, 45, 3256.
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Chemically modified electrode surfaces for CO2 reduction
Carlo Nervi, Cunfa Sun, Valeriya Mironova, Roberto Gobetto
Department of Chemistry, University of Torino, via P. Giuria 7, 10125 Torino,
Italy, email: [email protected]
The reduction of CO2 into valuable chemicals is one of the most active current
research fields. The sustainable photoelectrochemical approach [1] ideally requires
the use of a suitable catalyst supported on the electrode surface. While the design,
synthesis, characterization and study of mechanistic aspects (i.e. also by
computational approaches) of a molecular “homogenenous” catalyst is easier, the
combination with an “heterogeneous” approach could improve the catalyst stability
and durability, making the CO2 conversion more feasible and appealing [2].
We chemically modified the
surface of a Glassy Carbon
Electrode (GCE) by Re and
Mn carbonyl bpy-type
complexes. Different
approaches, namely
electropolymerization of
thiophene-containing Re
complexes and reduction of
diazonium salts embedded
in Re(bpy-R)(CO)3Cl and
Mn(bpy-R)(CO)4Br deriva-
tives (where bpy-R is a
bipyridines-type ligand)
were explored. These
chemically modified
electrodes show an
interesting improvement on
the stability and TON (Turn Over Number) for the electrocatalytic reduction of CO2.
For example, the Figure shows the catalytic current enhancement over GCE after
electropolymerization of Re(2,2':5',2''-terthiophene)(CO)3Cl [3].
[1] a) Rongé, J.; Bosserez, T.; Martel, D.; Nervi, C.; Boarino, L.; Taulelle, F.; Decher, G.; Bordiga
S.; Martens, J. A. Chem. Soc. Rev. 2014, 43, 7963; b) Costentin, C.; Robert, M.; Saveant, J.
M. Chem. Soc. Rev. 2013, 42, 2423.
[2] a) Young, K. J.; Martini, L. A.; Milot, R. L.; Snoeberger III, R. C.; Batista, V. S.;
Schmuttenmaer, C. A.; Crabtree, R. H. Brudvig, G. W. Coord. Chem. Rev. 2012, 256, 2503; b) Sun, C.; Gobetto, R.; Nervi, C. New J. Chem. 2016, doi:10.1039/C5NJ03426D.
[3] Sun, C. Prosperini, S.; Quagliotto, P.; Viscardi, G.; Yoon, S. S.; Gobetto, R.; Nervi, C. Dalton
Trans. 2016, doi:10.1039/c5dt04491j.
-2.4 -2.2 -2.0 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2
-2000
-1500
-1000
-500
0
Cu
rre
nt (
A)
Potential (V)
Ar
CO2
FC in Ar stable
FC in CO2 1
st
Figure 1 CV in MeCN of the chemically modified GCE by Re(terthiophene)(CO)3Cl (Γ = 35.3×10–10 mol/cm2) at scan rate
of 0.2 V/s under Ar and under CO2.
OC sponsor
29
CIAOTECH PNO partner in REE4EU, Indus3Es
and MEMERE projects
Valentina Cinti
CiaoTech PNO, Via Pacini 11, 20131 Milano, Italy, e-mail: [email protected]
As innovation and technology transfer organisation, CiaoTech PNO is leading dissemination and exploitation activities in 3 EU SPIRE projects, ensuring the project impact among relevant stakeholders. The REE4EU project: Integrated high temperature
electrolysis and Ion liquid extraction for a strong and independent European rare earth elements supply chain, funded in the frame of Horizon 2020 TOPIC SPIRE-07-2015 under Grant Agreement n° 680507, will realize a breakthrough innovation in the field of recovery technologies for metals and other minerals. It will make available rare earth elements and rare earth alloys for magnet production by developing, for the first time at industrial scale, an efficient and cost effective method of extraction and a direct production route for rare earth alloys which will be achieved through in-process and end-of-Life permanent magnets as well as Ni metal hydride battery waste. It will develop, validate and demonstrate in 2 industrially relevant pilots an innovative rare earth alloys production route from permanent magnets and nickel metal hydride battery waste. Large quantities of waste heat are continuously rejected from industries. Most of this waste energy, however, is of low-quality and is not practical or economical to recover it with
current technologies. The Indus3Es project funded in the frame of Horizon 2020 TOPIC EE-18-2015: under Grant Agreement n° 680738 , will develop an innovative Absorption Heat Transformer (AHT) for this purpose, focused on low temperature waste heat recovery (below 130ºC, referred to a recovered waste heat source temperature). The Indus3Es System will effectively recover and revalorize almost 50% of the low temperature waste heat, increasing quality of the waste source to the required temperature and
reusing it again in the industrial process. The developed system will be demonstrated in real environment in Tüpras, the main petrochemical industry in Turkey, enabling to analyze besides integration aspects, operational and business issues. Indus3Es System will be defined and optimized for different specificities in different sectors and industrial processes, for which up-scaling of the demonstrated technology and replication studies will be performed. MEthane activation via integrated MEmbrane REactors (MEMERE) responds to the EU Horizon 2020 call SPIRE-05-2015 and is a research and innovation project aiming at methane activation towards C2+, funded under the Grant Agreement n° 636820 . It aims at the design, scale-up and validation of a novel membrane reactor for the direct conversion of methane into ethylene with integrated air separation. The focus of the project will be on the air separation through novel MIEC membranes integrated within a reactor operated at high temperature for OCM allowing integration of different process steps in a single multifunctional unit and achieving significantly higher yields in comparison with the conventional reactor technologies, combined with improved energy efficiency. The results of MEMERE will contribute to the competitiveness of the European process industry in a field (ethylene production) that is an important part of the chemical sector.
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Electrocatalytic CO2 reduction by Mn(bpy-R)(CO)3Br complexes
Roberto Gobetto, Claudio Cometto, Federico Franco, Luca Nencini, Carlo Nervi
Department of Chemistry, University of Torino, Via P. Giuria 7, 10125 Torino,
Italy, email: [email protected]
The sustainability and encouraging performance displayed by the electrochemical
conversion of carbon dioxide into value-added chemicals, which is mediated by
transition metal complexes, has attracted growing interest in recent years [1,2]. Many
organometallic catalysts have been found to selectively reduce CO2 into two-electron
products, such as CO and HCOOH, in non-aqueous systems. The development of
manganese organometallic complexes for use in catalytic electrochemical CO2
reduction was boosted by a seminal publication by Chardon-Noblat, Deronzier et al.
[3]. They reported that the Mn(I) complexes such as Mn (bipy)(CO)3Br are able to
catalyze the electrochemical reduction of CO2 into CO in the presence of water as a
weak Brönsted acid, with a negligible electrochemical proton reduction. Reduction
process proceeds with overpotentials being ca. 0.35–0.4V lower than those of
rhenium analogs, namely fac-Re(bipy)(CO)3Br, keeping a similar level of selectivity
and robustness.
The availability of local proton sources is known to greatly enhance the selectivity
and the redox catalytic activity for CO2 reduction to CO. For this reason we have
synthesized novel polypyridyl Mn(I) catalysts (e.g. [Mn(dhbpy)(CO)3Br] (dhbpy =
4-phenyl 6-(1,3-dihydroxybenzen-2-yl)-2,2'-bipyridine) containing acidic OH
groups in proximity of the purported metal binding site for CO2 redox catalysis.
The new Mn complexes show enhanced catalytic activity and clear mechanistic
pathway [4].
[1] Ronge´, J.; Bosserez, T.; Martel, D.; Nervi, C.; Boarino, L.; Taulelle, F.; Decher, G.; Bordiga
S.; Martens, J. A. Chem. Soc. Rev. 2014, 43, 7963. [2] Saveant, J. M. Chem. Rev. 2008, 108, 2348.
[3] Bourrez, M.; Molton, F.; Chardon-Noblat, S.; Deronzier, A. Angew. Chem. Int. Ed. 2011, 50,
9903.
[4] Franco, F.; Cometto, C.; Ferrero Vallana, F.; Sordello, F.; Minero, C.; Priola, E.; Nervi, C.;
Gobetto R. Chem. Commun. 2014, 50, 14670.
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31
MediaChrom: exploring a new family of pyrimidoindolone-based
polarity-sensitive dyes
Monica Dell’Acqua1, Giorgio Abbiati1, Luca Ronda2, Riccardo Piano2, Sara Pellegrino1,
Elisabetta Rossi1, Francesca Clerici1, Andrea Mozzarelli3, Maria Luisa Gelmi1
1 DiSFarm - Sez. Chim. Gen. e Org. “A. Marchesini”, Università degli Studi di
Milano, Via Venezian, 21, 20133 Milano, Italy, email:
[email protected] 2 Dipartimento di Neuroscienze e 3 Dipartimento di Farmacia, Università degli
Studi di Parma, Parco Area delle Scienze, 23/A, 43124 Parma, Italy
The modern biological research asks for a continuous development of new
fluorescent dyes characterized by improved performances and suitable to be used as
markers or probes [1]. A particular class of dyes, called polarity-sensitive dyes have
the unique features to display a different emission maximum as a function of the
polarity of their molecular environment (media). This peculiarity makes polarity-
sensitive dyes the ideal probes to monitor the local properties of particular cell
districts as well as different type of biomolecular interactions [2]. Since many years,
we have been interested in the development of new strategies for the synthesis and
the functionalization of indoles and polycyclic indole-based heterocycles. In this
context, we reported a domino approach to pyrimidoindolones [3] that displayed
interesting fluorescence properties. Starting from these findings, a small library of
original polarity-sensitive fluorescent dyes, nicknamed MediaChrom, has been
prepared [4]. They are characterized by a pyrimidoindolone core fitted out with a
conjugated push-pull system, and a linker for an easy coupling with biomolecules.
The synthetic strategy involves a highly chemo- and regioselective gold catalyzed
cycloisomerization as key step. The photophysical properties of MediaChrom dyes
have been evaluated, and some potential biological applications have been spottily
investigated.
[1] Lakowicz, J. R. Principles of Fluorescence Spectroscopy, 3rd ed.; Springer: New York, 2006. [2] Klymchenko, A. S.; Mely, Y. In: Progress in Molecular Biology and Translational Science,
Morris, M.C. Editor(s), Academic Press, 2013, Vol. 113, Cap. 2, 35.
[3] Facoetti, D.; Abbiati, G.; d’Avolio, L.; Ackermann, L.; Rossi, E. Synlett 2009, 2273.
[4] Dell'Acqua, M.; Ronda, L.; Piano, R.; Pellegrino, S.; Clerici, F.; Rossi, E.; Mozzarelli, A.;
Gelmi, M. L.; Abbiati, G. J. Org. Chem. 2015, 21, 10939. This work has been supported by Fondazione Cariplo, Grant No. 2012-0907.
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Synthesis of 3,3’-substituted-2,2’-biindoles and 2,2’-substituted-
3,3’-biindoles: high valuable compounds for material science
Andrea Penoni1, Tiziana Benincori1, Patrizia R. Mussini2, Serena Arnaboldi2,
Roberto Cirilli3
1 Dipartimento di Scienza e Alta Tecnologia, Università degli Studi dell’Insubria,
via Valleggio 9, 22100 - Como, Italy, email: [email protected] 2 Dipartimento di Chimica and C.I.Ma.I.Na, Università degli Studi di Milano, via
Golgi 19, 20133 – Milano, Italy 3 Dipartimento del Farmaco, Istituto Superiore di Sanità, viale Regina Elena 299,
00161 – Roma, Italy
Sannicolò and coworkers investigated very recently electroactive chiral
polyheterocycles, where chirality is not external to the electroactive backbone but
inherent to it, and results from a torsion generated by the periodic presence of
atropisomeric, conjugatively active biheteroaromatic scaffolds, (3,3’-
bithianaphthene) [1-3]. Linear conjugated oligothiophenes are ubiquitous in
technologically advanced optoelectronic devices.
More recently, with the aim to investigate the properties of indole derivatives
substituted with oligothiophene frameworks we afforded two different constitutional
isomers by methodologies introduced by Arcadi and coworkers [4,5].
[1] Sannicolò, F.; Arnaboldi, S.; Benincori, T.; Bonometti, V.; Cirilli, R.; Dunsch, L.; Kutner, W.;
Longhi, G.; Mussini, P. R.; Panigati, M.; Pierini, M.; Rizzo, S. Angew. Chem. Int. Ed. 2014,
53, 2623.
[2] Sannicolò, F.; Mussini, P. R.; Benincori, T.; Cirilli, R.; Abbate, S.; Arnaboldi, S.; Casolo, S.;
Castiglioni, E.; Longhi, G.; Martinazzo, R.; Panigati, M.; Pappini, M.; Quartapelle Procopio,
E.; Rizzo, S. Chem. Eur. J. 2014, 20, 15298.
[3] Sannicolò, F.; Mussini, P. R.; Arnaboldi, S.; Quartapelle Procopio, E.; Panigati, M.;
Martinazzo, R.; Selli, E.; Chiarello, G. L.; Benincori, T.; Longhi, G.; Rizzo, S.; Cirilli, R.;
Penoni, A. WO 2015/177763.
[4] Abbiati, G.; Arcadi, A.; Beccalli, E.; Bianchi, G.; Marnelli, F.; Rossi, E. Tetrahedron 2006, 62, 3033.
[5] Arcadi, A.; Chiarini, M.; D’Anniballe, G, Marinelli, F.; Pietropaolo, E. Org. Lett. 2014, 16,
1736.
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Bond forming reactions involving isocyanides mediated by diiron
complexes
Valerio Zanotti1, Stefano Zacchini1, Fabio Marchetti2
1 Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna ,
Viale Risorgimento 4 , 40136 Bologna, Italy, email: [email protected] 2 Dipartimento di Chimica e Chimica Industriale, Università di Pisa,
via Moruzzi 3, 56124 Pisa, Italy
Isocyanides are extremely valuable building blocks for the construction of complex
molecular structures and, in particular, of heterocycles. Metal mediated reactions
involving isocyanides include CNR insertion into different metal-element bond and
this field is largely dominated by the use of Pd complexes [1]. Here, we report on
reactions involving isocyanides which occur at diiron complexes displaying the
frame: [Fe2Cp2(CO)(L)2]. Our interest in diiron complexes is aimed at finding new
bond forming reactions potential able to provide alternatives to toxic and/or rare
metals [2]. We have fond that diiron complexes can effectively promote the coupling
of isocyanides with coordinated ligands, including bridging carbynes, CO,
isocyanides. The assembling is generally initiated by a nucleophilc addition at a
coordinated ligand, which promote a cascade sequence involving other coordinated
fragments. One example is shown in following figure [3].
Other examples involve the coupling of two isocyanides via C-N bond formation
promoted by acetilide addition [4], and isocyanide-carbyne coupling activated by
hydride addition [5].
[1] Boyarskiy, V. P. et al. Chem Rev. 2015, 115, 2698.
[2] Mazzoni, R.; Salmi, M.; Zanotti, V. Chem. Eur. J. 2012, 18, 10174.
[3] Marchetti, F.; Zacchini, S.; Zanotti, V. Chem. Comm 2015, 51, 8101.
[4] Marchetti, F.; Zacchini, S.; Zanotti, V. Organometallics 2015, 34, 3658. [5] Marchetti, F.; Zacchini, S.; Zanotti, V. Organometallics 2014, 33, 3990.
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Pd-catalysed synthesis of blue organic dyes and their application as
sensitizers for near-IR absorbing dye-sensitized solar cells
Alessio Dessì1, Matteo Bartolini2, Massimo Calamante1,2, Alessandro Mordini1,2,
Maurizio Peruzzini1, Adalgisa Sinicropi3, Riccardo Basosi3, Maurizio Taddei3,
Lorenzo Zani1, Gianna Reginato1
1Istituto di Chimica dei Composti Organometallici (CNR–ICCOM), Via Madonna
del Piano 10, 50019 Sesto Fiorentino (FI), Italy, email:
mailto:[email protected] 2Dipartimento di Chimica “U. Schiff”, Università degli Studi di Firenze, Via della
Lastruccia 13, 50019 Sesto Fiorentino (FI), Italy 3Dipartimento di Biotecnologie, Chimica e Farmacia, Università degli Studi di
Siena, Via A. Moro 2, 53100 Siena, Italy
Since their discovery in 1991 [1], Dye-Sensitized Solar Cells (DSSC) have been
considered a very promising technology to convert solar energy in electric current
due to their low cost of production, their innovative aesthetic properties and their
easy integration in buildings and objects [2]. The dye, which can be a completely
organic molecule, is the photoactive material and is considered the heart of a DSSC
[3]. The introduction of an auxiliary acceptor group inside the classical D-π-A motif
of the organic sensitizers can play a key role to achieve dyes with a very intense and
broad light absorption spectrum and high incident photon-to-current conversion
efficiencies [4]. Aiming to this goal, we selected as new
auxiliary acceptor group the (E)-3,3’-bifuranylidene-2,2’-dione
(Figure 1) [5], a strong electron-withdrawing system which was
firstly prepared in 1882 [6]. The synthesis of this dye has been
optimized and its derivatization using Pd-catalysed cross-
coupling reactions has been firstly accomplished. Then, two new
D-A-π-A dyes containing the (E)-3,3’-bifuranylidene-2,2’-
dione as auxiliary acceptor group have been designed,
synthesized and characterized: the two new dyes showed an
intense blue color in solution and, when adsorbed on a TiO2 electrode, both a broad
absorption of the red/near-infrared light between 500 and 800 nm and right
electrochemical potentials for a proper use in DSSCs.
[1] O‘Reagan, B.; Grätzel, M. Nature 1991, 353, 737.
[2] Dye-sensitized solar cells (Ed.: K. Kalyanasundaram), EPFL Press, Lausanne 2010.
[3] Hagfeldt, A.; Boschloo, G.; Sun. L.; Kloo, L.; Petterson, H. Chem. Rev. 2010, 110, 6595.
[4] Wu, Y.; Zhu, W. H. Chem. Soc. Rev. 2013, 42, 2039.
[5] Kingsberg, E. Chem. Rev. 1954, 54, 59.
[6] Von Pechmann, H. Ber. 1882, 15, 885.
Figure 1. Structure of
(E)-3,3’-bifuranylidene-
2,2’-dione
OC9
35
Recent developments on gold(III) complexes with
di(N-heterocyclic carbene) ligands
Marco Baron1, Marco Monticelli1, Andrea Biffis1, Cristina Tubaro1, Claudia
Graiff2
1 Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo 1, 35131
Padova, Italy, email: [email protected] 2 Dipartimento di Chimica, Università di Parma , Viale delle scienze 17/a, 43124,
Parma, Italy
Nowadays gold complexes represent a hot topic in organometallic chemistry, since
they are attractive both for their properties (e.g. the presence of aurophilic
interaction) and for their application in fields like catalysis, medicinal chemistry and
material science [1]. N-heterocyclic carbenes (NHCs) are privileged ligands for gold
centers as highlighted both from experimental and theoretical studies [2]. We are
interested in the preparation and study of gold complexes with di(NHC) ligands, both
in +I and +III oxidation state. The highest oxidation state of gold has been up to now
overlooked with respect to the more popular gold(I), basically because gold(III) has
an higher oxidant power and its organometallic complexes are characterized by a
lower stability [3]. Here we report on two different successful protocols for the
synthesis of novel gold(III) complexes with di(NHC) ligands.
[1] a) Díez-González, S.; Marion, N.; Nolan, S.P. Chem. Rev. 2009, 109, 3612; b) Bertrand, B.;
Casini, A. Dalton Trans. 2014, 43, 4209; c) Barnard, P.J.; Berners-Price, S.J. Coord. Chem.
Rev. 2007, 251, 1889; d) Biffis, A; Baron, M.; Tubaro, C. Adv. Organomet. Chem. 2015, 63,
203. [2] a) Muniz, J.; Wang,C.; Pyykkö, P. Chem. Eur. J. 2011, 17, 368; b) Baron, M.; Tubaro, C.;
Basato, M.; Biffis, A.; Graiff, C.; Poater, A.; Cavallo, L.; Armaroli, N.; Accorsi, G. Inorg.
Chem. 2012, 51, 1778.
[3] a) Zhu, S.; Liang, R.; Jiang, H. Tetrahedron 2012, 68, 7949; b) Lu, Z.; Cramer, S. A.; Jenkins,
D. M. Chem. Sci. 2012, 3, 3081; c) Hung, F.-F.; To, W.-T.; Zhang J.-J.; Ma, C.; Wong, W.-
Y.; Che, C.-M. Chem. Eur. J. 2014, 20, 8604.
OC10
36
Design and synthesis of multifunctional fluorescent magnetic
nanoparticles for promising biomedical applications
Chiara Lambruschini1, Silvia Villa1, Luca Banfi1, Fabio Canepa1, Fabio Morana1,
Annalisa Relini2, Paola Riani1, Renata Riva1 and Fulvio Silvetti1
1 Department of Chemistry and Industrial Chemistry, University of Genova,
Via Dodecaneso 31, 16146 Genova, Italy, email:
[email protected] 2 Department of Physics, University of Genova, Via Dodecaneso 33, 16146
Genova, Italy
Multifunctional nanoprobes combining magnetic nanoparticles (MNPs) with organic
dyes have attracted great interest due to their promising applications in biomedical
field. Among the wide selection of different nanoprobes, superparamagnetic iron
oxide nanoparticles (SPIONs),[1] loaded with different functionalities, have a very
promising application in the drug delivery therapy.
Our work is focused on the study of SPIONs conjugated to a fluorescent tag through
a tripeptide linker.[2,3] This peculiar system has been designed to be cleaved by
specific enzymes, which are overexpressed in tumor cells, with the resulting release
of the fluorescent tag. Therefore, this original system could find application in the
imaging diagnostic and the drug delivery fields.
SPIONs conjugated with a fluorescent tag which can be released by enzymes for application in the
biomedical field.
Herein, we present the synthesis and the characterization of the two components (the
magnetite MNPs and the tripeptide linked to a fluorescent tag) and the study of their
conjugation. Furthermore, we present the preliminary results of the enzymatic
cleavage, as proof of concept of our project.
[1] Mody V. V. et al. Appl Nanosci 2014, 4, 385.
[2] Banfi L. et al. Eur. J. Org. Chem. 2003, 1319.
[3] Eisenbrand G. et al. Synthesis 1996, 1246.
OC11
37
New nickel-phosphorus homoleptic carbonyl clusters: synthesis,
characterization, and catalytic properties
Chiara Capacci, Cristina Femoni, Maria Carmela Iapalucci, Stefano Zacchini
“Toso Montanari” Industrial Chemistry Department, School of Science, University
of Bologna, Viale del Risorgimento 4, 40136 Bologna, Italy, email:
Nickel phosphides represent a new class of hydroprocessing catalysts, which have
emerged as a promising group of high-activity, stable catalysts [1]. Moreover, it is
known that carbonyl clusters can be used as precursors for the production of
nanoparticles [2]. Therefore, the synthesis of new nickel-phosphorus carbonyl
clusters was attempted. No homoleptic species
were known in the literature, and only examples
with alkyl groups as well as carbonyl ligands were
reported [3]. The reaction between the dianionic
precursor [Ni6(CO)12]2- and phosphorous halides,
such as PCl3 and POCl3, in various conditions
allowed to obtained new homoleptic species.
[Ni11P(CO)18]3-, [Ni14P2(CO)22]
2- (shown in Figure
A) [Ni23-xP2(CO)30-x]4- (x = 0, 1),
[HnNi31P4(CO)39](6-n)- (n = 1, 2), and
[Ni39P3(CO)44]6- (shown in Figure B) were
characterized. Their reactivity was analyzed,
revealing interesting features. Some of these
compounds were suitable as precursors for
heteroatomical nanoparticles, both supported and
non-supported. The catalytic behavior of these
new materials proved to be modest, and in the
future will need to be further investigated.
[1] a) Oyama, S. T.; Journal of Catalysis 2003, 216, 343; b) Lee, Y. K.; Shu, Y.; Oyama, S. T.
Appl. Catal. A: Gen. 2007, 322, 191; c) Chen, J.; Chen, Y.; Yang, Q.; Li, K.; Yao, C. Catal.
Commun. 2010, 11, 571; d) Liu, P.; Rodriguez, J. A.; Takahashi, Y.; Nakamura, K. J. Catal.
2009, 262, 294; e) Liu, P.; Rodriguez, J. A. J. Am. Chem. Soc. 2005, 127, 14871.
[2] Albonetti, S.; Bonelli, R.; Mengou, J. E.; Femoni, C.; Tiozzo, C.; Zacchini, S.; Trifirò, F.
Catalysis Today 2008, 137, 483.
[3] Rieck, D. F.; Gavney, J. A.; Norman, R. L.; Hayashi, R. K.; Dahl, L. F. J. Am. Chem. Soc.
1992, 114, 10369.
OC12
38
Pyrazole-based ligands: a useful tool for bioinorganic,
organometallic and material chemistry
Claudio Pettinari1, Fabio Marchetti2, Riccardo Pettinari1, Agnese Petrini1, Nello
Mosca1, Corrado Di Nicola2, Jessica Palmucci1, Francesca Condello1
1 University of Camerino, Scuola di Scienze del Farmaco e dei Prodotti della
Salute, via S. Agostino 1, 62032 Camerino, Italy, email:
[email protected] 2 University of Camerino, Scuola di Scienze e Tecnologie, via S. Agostino 1, 62032
Camerino, Italy
Pyrazole-based ligands are widely used in catalysis and in bioinorganic,
organometallic and material chemistry. Their success is due to the fact that
introduction of appropriate substituents on the heterocyclic rings allows extensive
control over the steric demand of the ligands. This could yield a different ability to
stabilize reactive complex fragments. Metal complexes bearing these ligands exhibit
a broad range of catalytic and stoichiometric reactivity. Here we describe recent
results obtained utilizing scorpionate and related ligands. Recent advances in
homogenous catalysis, as successful application of diverse metal-pyrazolylborate
systems to easy carbon-halogen (C-X) bonds and alkane catalytic functionalization;
in bioinorganic chemistry, as mimetic of coordination environments found in the
active sites of metalloenzymes; in the synthesis of poly(pyrazole)- and
poly(pyrazolate)-based coordination polymers, built up with selected transition
metals – namely copper, zinc and silver will be described in detail. The description
of the complexes will be complemented by information on their thermal behaviour,
main structural aspects and, whenever investigated, their functional properties [1].
[1] Pettinari, C; Pettinari, R; Marchetti, F. Adv. Organomet. Chem. 2016, in press, DOI:
10.1016/bs.adomc.2016.01.002.
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39
Rapid one-pot synthesis of heterocycles by sequentially palladium-
catalysed one-pot processes
Alissa C. Götzinger, Corinna Hoppe, Thomas J. J. Müller
Heinrich Heine Universität, Universitätsstraße 1, 40225 Düsseldorf, Germany,
email: [email protected]
Unsymmetric alkynes are valuable building blocks in heterocycle synthesis that can
also exhibit interesting properties for applications in molecular electronics. The most
common approach to this substance class requires three steps, proceeding via the
Sonogashira reaction of an aryl halide with trimethylsilyl acetylene, followed by
deprotection and coupling with a second aryl halide or aroyl chloride [1].
We herein present a protecting-group free, sequentially palladium-catalysed three
component approach to diarylalkynes and alkynones. Terminal alkynes are generated
in situ by palladium-catalysed coupling of aryl iodides with ethynyl magnesium
bromide [2], followed by Sonogashira coupling with no further addition of palladium
catalyst. The modular nature of the reaction, readily available starting materials, mild
reaction conditions, and short reaction times allow for the quick and convenient
synthesis of a large variety of target molecules [3].
The sequence can be extended by cyclocondensation of the alkynones intermediates
with dinucleophiles. A three step, four component one-pot synthesis of pyrazole [4]
and pyrimidine [5] derivatives was successfully established using hydrazine
derivatives and benzamidinium salts, respectively.
In summary, we disclose a convenient and versatile sequentially palladium-catalysed
strategy for the synthesis of unsymmetric alkynes and heterocycles. The reaction
proceeds with a large variety of substrates and can be modified and extended to give
access to different target molecules. No protecting groups are necessary and all
reactants and catalysts are readily available and easy to handle.
[1] Chinchilla, R.; Nájera, C. Chem. Rev. 2007, 107, 874.
[2] Negishi, E.-i.; Kotora, M.; Xu, C. J. Org. Chem. 1997, 62, 8957.
[3] Götzinger, A. C.; Müller, T. J. J. Org. Biomol. Chem. 2016, in press.
[4] Willy, B.; Müller, T. J. J. Eur. J. Org. Chem. 2008, 24, 4157.
[5] a) Karpov, A. S.; Müller, T. J. J. Synthesis 2003, 2815; b) Boersch, C.; Merkul, E.; Müller, T.
J. J. Angew. Chem. Int. Ed. 2011, 50, 10448.
OC14
40
Supramolecular interactions for highly selective transition-metal
catalysis
Umberto Piarulli
Università degli Studi dell’Insubria, Dipartimento di Scienza e Alta Tecnologia,
Via Valleggio, 11, 22100 Como, Italy, email: [email protected]
In the last decade, supramolecular approaches to the development of new ligands for
asymmetric catalysis have gained momentum [1]. The term 'supramolecular ligand'
encompasses all the ligands possessing, besides the atom(s) coordinating the
catalytic metal, an additional functionality capable of non-covalent interactions
(mainly hydrogen or coordinative bonds) which can play the following role: (i) self-
assemble two monodentate ligands to form a so-called 'supramolecular bidentate
ligand'; (ii) bind the substrate(s) in proximity to the catalytic metal center in analogy
to metalloenzymes. Both these approaches cause reduced degrees of freedom in the
catalytically active metal complexes, which is expected to result in more pre-
organised systems with better capacity of controlling the metal-catalysed reaction.
Herein we present our approaches of the application of supramolecular interactions
to rhodium, catalyzed hydrogenation of functionalized olefins [2] and the iron
catalyzed hydrogenation of ketones [3].
[1] Carboni, S.; Gennari, C.; Pignataro, L.; Piarulli, U. Dalton Trans. 2011, 40, 4355.
[2] Pignataro, L.; Boghi, M.; Civera, M.; Carboni, S.; Piarulli, U.; Gennari C. Chem. Eur. J. 2012,
18, 1383; b) Pignataro, L.; Bovio, C.; Civera, M.; Piarulli, U.; Gennari C. Chem. Eur. J. 2012,
18, 10368. [3] Gajewski, P.; Renom-Carrasco, M.; Vailati Facchini, S.; Pignataro, L.; Lefort, L.; De Vries,
J.G.; Ferraccioli, R; Piarulli, U.; Gennari, C. Eur. J. Org. Chem. 2015, 5526.
OC15
41
Highly conjugated blue dimers of platinum(II)
Roberto Esposito1, Luisa Calvanese1, Maria Elena Cucciolito1, Gabriella D’Auria1,
Lucia Falcigno1, Valentina Fiorini2, Prisco Pezzella1, Giuseppina Roviello3,
Francesco Ruffo1, Stefano Stagni2, Giovanni Talarico1
1 Università di Napoli “Federico II”, Italy, email: [email protected]
2 Università di Bologna, Italy 3 Università di Napoli “Parthenope”, Italy
Olefin compounds of type I [1], containing an N,N’-imino,amide ligand, have been
found to dimerize spontaneously in solution yielding dinuclear complexes II.
The extended conjugation within the
molecules produce an intense blue color,
and the properties of the compounds are
currently investigated through NMR
spectroscopy, optical measurements and
theoretical calculations.
The solid state structure of a representative
compound (R= H) has been solved.
The mechanism of formation of these
species is also under investigation.
[1] Ruffo, F. et al. Organometallics 2004, 23, 2137.
OC16
42
Ferrocenylporphyrins: from synthesis to photoelectrochemical
dioxygen activation
Valeria Conte, Federica Sabuzi, Martina Tiravia, Andrea Vecchi, Mariano Venanzi,
Emanuela Gatto, Barbara Floris, Pierluca Galloni
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata,
Via della Ricerca Scientifica, 00133, Roma, Italy, email:
Tetraferrocenylporphyrins (TFcPs) are a class of compounds where the porphyrin
macrocycle is functionalized with a ferrocenyl group on each of the four meso
positions. TFcPs exhibit interesting electrochemical properties mostly due to
electronic communication between the ferrocenyl substituents and the porphyrin
core [1], making them
suitable for the
construction of
molecular electronic
devices. With this aim,
synthesis of novel
substituted-TFcP has
been performed, to
prepare Self
Assembled
Monolayers and
Langmuir-Blodgett
mono- and multilayers of TFcPs on gold and ITO surfaces. Interestingly, TFcPs
yielded stable and densely packed films. Electrochemical and photoelectrochemical
properties of the resulting modified electrodes were evaluated and photocurrent
generation experiments have been performed showing an interesting, electrolyte-
tunable photo-catalytic activity toward dioxygen even at zero applied bias potential
[2-4].
[1] Nemykin, V. N.; Rohde, G. T.; Barrett, C. D.; Hadt, R. G.; Bizzarri, C.; Galloni, P.; Floris, B.;
Nowik, I.; Herber, R. H.; Marrani, A. G.; Zanoni, R.; Loim, N. M. J. Am. Chem. Soc. 2009,
131, 14969.
[2] Vecchi, A.; Gatto, E.; Floris, B.; Conte, V.; Venanzi, M.; Nemykin, V. N.; Galloni, P. Chem.
Commun. 2012, 48, 5145.
[3] Vecchi, A.; Erickson, N.R.; Sabin, J.R.; Floris, B.; Conte, V.; Venanzi, M.; Galloni, P.; Nemykin, V. Chem. Eur. J. 2015, 21, 269.
[4] Sabuzi, F.; Tiravia, M.; Vecchi, A.; Gatto, E.; Venanzi, M.; Floris, B.; Conte, V.; Galloni, P.
submitted.
OC17
43
Silver(I) catalyzed Henry reaction
Alessandro Caselli1, Giorgio Tseberlidis1, Daniele Valcarenghi1, Giorgio Abbiati2,
Monica Dell’Acqua2
1 Dipartimento di Chimica, Università degli Studi di Milano, via Golgi 19 – 20133
Milano, Italy, email: [email protected] 2 DISFARM, Sezione di Chimica Generale e Organica “A. Marchesini”, Università
degli Studi di Milano, Via Venezian, 21 – 20133 Milano, Italy
Nitroalkanes are important reagents not only due to their propensity to undergo easy
-dealkylation but also for their facile interconversion to other organic functional
groups. Even weak bases are capable to abstract the proton in -position of a nitro
group (pKa 9) and the nucleophilic attack of the generated nitronate anion to a
carbonyl compound to give a -nitro alcohol is referred as the Henry (or nitroaldol)
reaction. Although more than one century old, this reaction is still to be considered
one of the most important example of an atom-economy transformation.
In the past few years, our attention has turned to the
introduction of a pyridine moiety into the skeleton of
tetraaza-macrocycles, with the aim to obtain ligands
with increased conformational rigidity and different
basicity. The copper(I) complexes of these pyridine-
containing ligands (Pc-L) have been successfully
employed in catalysis[1] and have shown good
activities in the Henry reaction[2]. We have recently
reported the full characterization of the corresponding
[Silver(I)(Pyridine-Containing Ligand)], and we have demonstrated their catalytic
activity in the regiospecific synthesis of 1-alkoxy-isochromenes under mild
conditions and in the microwave enhanced A3-coupling[3]. Compared with simple
silver salts, the great advantage of those [Ag(I)(Pc-L)] complexes is their solubility,
ease of handling and enhanced stability. Prompted by the results obtained, we were
intrigued to see if our well defined silver(I) complexes were able to act as catalyst
also for the Henry reaction. As a result of this study, we found that [Ag(I)(Pc-L)]
complexes can actually activate the aldehyde toward the nitronate nucleophilic
attack, in the first example of a silver catalyzed Henry reaction. Since the Henry
reaction, especially in the asymmetric version, has provided a good platform for
testing the dual activation of metal/base catalysts, we have modified our ligands in
order to attach in the proper position a suitable base to facilitate the reaction.
[1] Castano, B. et al. Green Chem. 2014, 16, 3202.
[2] Castano, B. et al. Appl. Organomet. Chem. 2011, 25, 824.
[3] a) Pedrazzini, T. et al. Eur. J. Inorg. Chem. 2015, 5089; b) Dell’Acqua, M. et al. J. Org. Chem.
2014, 79, 3494; c) Trose, M. et al. J. Org. Chem. 2014, 79, 7311.
OC19
44
‘Totem’ C2-symmetrical iron(III) porphyrin complexes to
stereoselectively promote alkene cyclopropanation
Daniela Intrieri1, Emma Gallo1, Daniela Maria Carminati1, Lucio Toma2, Stéphane
Le Gac3, Bernard Boitrel3
1 Department of Chemistry, Università degli Studi di Milano, Via C. Golgi 19,
20133 Milano, Italy, email: [email protected] 2 Department of Chemistry, Università di Pavia, Via Taramelli 12, 27100 Pavia,
Italy. 3 Institut des Sciences Chimiques de Rennes, Université de Rennes 1, 263 avenue
du Général Leclerc, 35042 Rennes Cedex, France.
The stereoselective synthesis of cyclopropanes is an important issue in synthetic
chemistry due to the relevance of the three-member carbon rings [1]. The one pot
reaction of diazo compounds with alkenes represents a sustainable methodology to
achieve cyclopropanes due to the formation of N2 as
the only stoichiometric by-product. The reaction is
efficiently catalysed by metal porphyrins which
promote the synthesis of cyclopropanes with
excellent diastereo- and enantioselectivities [2]. The
two iron complexes 1Fe and 2Fe are good catalysts
for the alkene cyclopropanation, both of which have
a C2 axis within the porphyrin plane and exhibit an
open space on each side for the substrate access.
Complex 1Fe displays a pre-organized structure
responsible for excellent trans-diastereoselectivities (94-99%) in alkene
cyclopropanations while the presence of chiral moieties in 2Fe allowed to perform
the reactions also with very good enantioselectivity (up to 87%) [3]. Experimental
data disclosed that each ‘totem’ portion of 2Fe has a specific catalytic role: i) the
porphyrin core containing the active iron centre is in charge of activating the diazo
compound; ii) benzylic moieties are responsible for the reaction diasteroselectivity
and iii) the two chiral binaphthyl groups allow the enantioselective synthesis of
cyclopropanes. The study of the reaction scope revealed that both 1Fe and 2Fe
catalysts were active in promoting the cyclopropanation of several olefins by
differently substituted diazo compounds.
[1] a) Carson, C. A.; Kerr, M. A. Chem. Soc. Rev. 2009, 38, 3051; b) Kumar, A. K. Int. J. Pharm.
Pharm. Sci. 2013, 5, 467.
[2] Intrieri, D.; Carminati, D. M.; Gallo, E. ‘Recent Advances in Metal Porphyrinoid-Catalyzed
Nitrene and Carbene Transfer Reactions’ In Handbook of Porphyrin Science; eds. Kadish, K.
M.; Smith, K. M.; Guilard, R.; World Scientific Publishing Co. Pte. Ltd. in press.
[3] Intrieri, D.; Le Gac, S.; Caselli, A.; Rose, E.; Boitrel, B.; Gallo, E. Chem. Commun. 2014, 50, 1811.
OC19
45
Highly convergent synthesis of intensively blue emissive furo[2,3-
c]isoquinolines by a palladium-catalyzed cyclization cascade of
unsaturated Ugi products
Manuel Anselmo1, Lisa Moni1, Charlotte F. Gers-Panther2, Thomas J. J. Müller2,
Renata Riva1
1 Università degli Studi di Genova, Dipartimento di Chimica e Chimica Industriale,
Via Dodecaneso 31, 16146, Genova, Italy, email: mailto:[email protected] 2 Institut für Organische Chemie und Makromoleculare Chemie Heinrich-Heine-
Universität, Universitätsstraße 1, 40225 Düsseldorf, Germany
A convergent and diversity-oriented approach to the unusual furo[2,3-c] isoquinoline
scaffold is presented [1]. This serendipity-driven approach is characterized by an Ugi
multicomponent reaction [2], which gives the substrate for a palladium-catalyzed
insertion-alkynilation-cycloisomerization cascade to provide the furo[2,3-
c]isoquinolines in moderate to high yields.
Upon UV excitation, all representatives are intensively blue luminescent, as
observed by the naked eye, and quantitative fluorescence spectroscopy reveals a
considerable effect of the substitution pattern on the quantum yields [3].
[1] Moni, L.; Gers-Panther, C. F.; Anselmo, M.; Müller T. J. J.; Riva, R. Chem. Eur. J. 2016, 22,
2020.
[2] Ugi, I.; Meyr, R.; Fetzer, U.; Steinbruckner, C. Angew. Chem. 1959, 71, 386.
[3] Berlman, I. B. Handbook of Fluorescence Spectra of Aromatic Molecules, Academic Press, New York, 1971.
OC20
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σ-Donor and π-acceptor properties of substituted phenanthroline
ligands in [Mo(CO)4(phen*)] complexes: an ETS-NOCV analysis
Stefano Brenna, G. Attilio Ardizzoia, Michela Bea
University of Insubria, Dipartimento di Scienza e Alta Tecnologia, Via Valleggio 9,
22100 Como, Italy, email: [email protected]
Understanding the nature of metal-ligand bond in transition metal complexes is of
crucial importance in organometallic chemistry [1], hence both experimental [2a]
and theoretical [2b] studies have been performed in this direction over the last
decades. Among the different theoretical approaches, in the last years the ETS-
NOCV approach, where the Natural Orbital for Chemical Valence [3] are associated
with an energy decomposition analysis scheme (in particular with the Extended
Transition State[4] (ETS) method) has emerged as a very precious tool in shedding
light on donor-acceptor properties of ligands.
In the present study, we analyzed the bond between molybdenum and substituted
1,10-phenanthroline ligands in a series of [Mo(CO)4(phen*)] complexes, by
combining experimental data (νCO) with
results of DFT calculations. The outcomes
of the ETS-NOCV approach allowed to
quantify the energetic contribution of both
ligand-to-metal (Eσ) and metal-to-ligand
(Eπ) interaction. Bearing in mind the
mutual synergistic action of and
contributions, we plotted both the values
of Eσ and Eπ calculated for each
compound against the corresponding
experimental νCO (Figure on the left).
It has been introduced a new parameter
(Tphen) which comprises both Eσ and Eπ,
thus representing a possible descriptor for
the overall electronic contribution given by phenanthrolines to the metal/ligand
bond. This statement is corroborated by the linear correlation found between Tphen
and the νCO modes of [Mo(CO)4(phen*)] complexes, at least for those containing a
2,9-unsubstituted 1,10-phenanthroline.
[1] Frenking, G.; Frölich, N. Chem. Rev. 2000, 100, 717.
[2] a) Damon, P. L.; Liss, C. J.; Lewis, R. A.; Morochnik, S.; Szpunar, D. E.; Tesler, J.; Hayton,
T. W. Inorg. Chem. 2015, 54, 10081; b) Fey, N.; Orpen, A. G.; Harvey, J. N. Coord. Chem. Rev. 2009, 253, 704.
[3] a) Mitoraj, M. P.; Michalak, A. J. Mol. Model. 2007, 13, 347; b) Michalak, A.; Mitoraj, M. P.;
Ziegler, T. J. Phys. Chem. A 2008, 112, 1933.
[4] Ziegler, T.; Rauk, A. Theor. Chim. Acta 1977, 46, 1.
OC21
47
Iron complexes as effective photocatalysts for the asymmetric
alkylation of aldehydes
Luca Mengozzi1, Andrea Gualandi1, Noemi Vuerich1, Marc Beley,2 Philippe C.
Gros2, Pier Giorgio Cozzi1
1 Dipartimento di Chimica “G. Ciamician” ALMA MATER STUDIORUM,
Università di Bologna, Via Selmi 2, 40126, Bologna, Italy, email:
[email protected] 2 Université de Lorraine, CNRS, SRSMC, Boulevard des Aiguillettes, 54506,
Vandoeuvre-Lès-Nancy, France
We recently demonstrated that, under visible light irradiation, [Fe(bpy)3]2+ is able to
photocatalytically promote the enantioselective α-alkylation of aldehydes with
bromomalonates, activated α-bromoesters and α-bromoacetophenones [1]. The
extremely short lived excited state [2] of [Fe(bpy)3]2+ makes the single electron
transfer process, which generates radical II, rather inefficient. However thanks to a
very efficient radical chain process, we obtained results comparable to those
achieved with [Ru(bpy)3]2+, organic dyes or semiconductors. Recently carbene-iron
complexes [3], which show increased excited states lifetimes, were reported by some
of us and we are currently investigating their application in photocatalytic processes.
Moreover, we are exploring the use of modified MacMillan’s imidazolininones in
order to obtain more stable and efficient organocatalysts, with the aim to decrease
their loading.
[1] Gualandi, A.; Marchini, M.; Mengozzi, L.; Natali M.; Lucarini, M.; Ceroni, P.; Cozzi, P. G.
ACS Catalysis, 2015, 5927.
[2] Ferrere, S.; Gregg, B. A. J. Am. Chem. Soc. 1998, 120, 843.
[3] Duchanois, T.; Etienne, T.; Cebrián, C.; Liu, L.; Monari, A.; Beley, M.; Assfeld, X.; Haacke, S.; Gros P. C. Eur. J. Inorg. Chem. 2015, 2469.
OC22
48
Positional effect of a hydroxyl group on the activity of pyridyl-
carboxylate catalysts for water oxidation
Gabriel Menendez Rodriguez, Alberto Bucci, Gianfranco Bellachioma, Cristiano
Zuccaccia, Alceo Macchioni
Department of Chemistry, Biology and Biotechnology, Perugia University, Via
Elce di Sotto 8, 06123 Perugia, Italy, e-mail: [email protected]
The production of solar fuels, such as green and sustainable alternative to fossil fuels,
has become an unavoidable task for our society. Exploiting solar energy to make
happen endoergonic processes (hydrogen production and CO2 hydrogenation) using
the electrons and protons derived from the oxidation of water, appears to be a
promising solution. However, the efficiency of an artificial photosynthetic apparatus
based on such processes seems to be limited by the still unsatisfactory performance
of the water oxidation catalytic pool. Catalytic water oxidation has been investigated
using five Cp*Ir complexes; [Cp*Ir(pic)NO3] (where pic = 2-pyridinecarboxylic
acid), previously reported by us [1], and the closely related OH substituted, in all
positions of the pyridine ring. The effects
of the electron-donating –OH substituent
was evaluated using NaIO4 as an oxidant
at various pH conditions. Similar studies
have been recently performed by Himeda
and Papish [2,3], whose reported some
Cp*Ir WOCs which contain proton-
responsive ligands based on dihydroxy-
2,2′-bipyridine derivatives. They showed
that the introduction of the hydroxyl
groups, in particular positions of the bipy
rings, has a beneficial effect and strongly
increases the catalytic activity of WOCs.
We found that the effect exerted by the presence of the OH group on the catalytic
activity depends on the pH of the medium. At pH 5, the hydroxyl derivatives are
more active than the non-substituted compound, whereas, at pH 7, the opposite is
observed (Figure, pH = 7 by phosphate buffer, Ccat= 5 M, CNaIO4 = 20 mM). Kinetic
isotopic effects, reaction orders and the role the buffer system were investigated in
order to rationalize the observed behavior. The results will be discussed in this
contribution.
[1] Bucci A. et al. Organometallics, 2012, 31, 8071.
[2] Fujita E. et al. Phys. Chem. Chem. Phys. 2014, 16, 11976.
[3] Papish E.T. et al. Inorg. Chem. 2013, 52, 9175.
OC23
49
Catalytic properties of pyrazolato-based metal-organic
frameworks with exposed metal sites
Alessandro Cimino1, Simona Galli1, Angelo Maspero1, Juliana Velàsquez Ochoa2,
Carlo Lucarelli1
1 Dipartimento di Scienza ed Alta Tecnologia, Università degli Studi dell’Insubria,
Via Valleggio 11, Como, Italy, email: [email protected] 2 Dipartimento di Chimica Industriale, Università di Bologna, Viale del
Risorgimento 4, Bologna, Italy
Pyrazolato-based metal-organic frameworks (MOF) are a class of hybrid porous
solids that possess unique properties among the various classes of microporous and
mesoporous materials; MOFs are crystalline materials resulting from the reaction
between an organic linker and inorganic species, such as clusters or metal ions. The
linkage between these two partners generates a three dimensional framework whose
skeleton contains both organic and inorganic units linked by classical coordination
bonds.
This structures lead to a material with a huge
surface area. This kind of materials could
have exposed metal site, so they could be
used as heterogeneous catalysts. In this
context, this contribution details on the
catalytic activity of the MOF [Ni3(BTP)2][1],
obtained by coupling Ni(II) salts to the
tris(pyrazolato)-based ligand 1,3,5-tris(1H-
pyrazol-4-yl)benzene (H3BTP). We have
demonstrated, by IR evidence, the existence of guest-host interactions, coordination
of the substrate to the nickel, and the better catalytic activity compared to other
catalyst using milder conditions. Considerably, [Ni3(BTP)2] exhibits an expanded
sodalite-like framework with exposed metal sites and possesses a remarkable thermal
and chemical robustness, being stable in air up to 430 °C, and in boiling aqueous
solutions of pH 2 to 14 for at least two weeks.
[1] Colombo, V.; Galli, S.; Choi, J. H.; Han, G. D.; Maspero, A.; Palmisano, G.; Masciocchi, N.;
Long, J. R. Chem. Sci. 2011, 2, 1311.
OC24
50
Reductive cyclization of nitro compounds using CO surrogates:
formate esters at work
Dario Formenti, Francesco Ferretti, Fabio Ragaini
Dipartimento di Chimica – Università degli Studi di Milano, Via C. Golgi 19,
20133 Milano, Italy, email: [email protected]
Catalytic reductive cyclization of substituted aromatic nitro compounds represents a
valuable approach for the synthesis of N-containing heterocycles. Using gaseous CO
as the reductant is possible to selectively transform the nitro group into much more
reactive intermediates (such as nitroso compounds) that can further undergo inter or
intra-molecular amination reactions.1 Nevertheless, CO is a highly toxic molecule
whose handling requires the installation of expensive safety measures and high-
pressure equipments. In order to overcome this issue, we developed a synthetic
protocol in which formate esters (both alkyl and aryl) are employed as CO sources,
thus avoiding the use of pressurized gas.2 In particular phenyl formate was found to
be an excellent CO surrogate enabling the preparation of various substituted indoles
by Pd-catalyzed reductive cyclization of ortho-nitrostyrenes with excellent
selectivities. Notably, the transformation proceeds more efficiently than the
corresponding reaction carried out under gaseous CO conditions. In addition,
preliminary investigations devoted to the clarification of the reaction mechanism are
presented.
[1] Ragaini, F.; Cenini, S.; Gallo, E.; Caselli, A.; Fantauzzi, S. Curr. Org. Chem. 2006, 10, 1479.
[2] Konishi, H.; Manabe, K. Synlett 2014, 25, 1971.
51
POSTERS
P1
52
Heteroditopic diNHCs as novel ligands for transition metal centers
Marco Monticelli1,2, Cristina Tubaro1, Stéphane Bellemin-Laponnaz2
1 Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo
1, 35131, Padova, Italy, email: [email protected] 2 Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), CNRS-
Université de Strasbourg, UMR7504, 23 Rue du Loess BP 43, 67034, Strasbourg,
France
In the last years, di(N-heterocyclic carbene) ligands (diNHC) and the related
transition metal complexes have been widely studied and used for different
applications, spanning from catalysis to photochemistry or medicinal chemistry [1].
The basic structure of most diNHCs reported in the literature (the so-called normal
NHCs) consists of two imidazol-2-
ylidenes moieties linked by an
aliphatic or aromatic bridging group.
By changing the ligand scaffold it is
possible to tune the sterical and
electronical properties of the
coordinated metal centers; the same
goal can be easily reached also by
using, for example heteroditopic
diNHCs, i.e. ligands with two
different types of carbene moieties
like imidazol-2-ylidene and 1,2,3-
triazol-ylidene (nNHC/tzNHC). The
precursors of these diNHC ligands
can be easily obtained by insertion of
the triazole unit via click reaction between an alkyne-functionalized imidazole and
an organic azide [2,3]. In this work, two different diNHC precursors have been
obtained, functionalized in the nNHC backbone position (type A) or in the nitrogen
wingtip substituent (type B). The coordination properties of these ligands towards
late transition metals have been investigated; in particular the silver(I) complexes
could be obtained by reaction of the proligands with Ag2O. The diNHC ligand could
be then transferred successfully to different metal centres like gold(I), copper(I) or
ruthenium(II).
Preliminary results on the antiproliferative activity of the obtained complexes will
also be presented.
[1] Biffis, A.; Baron, M.; Tubaro, C. Adv. Organomet. Chem. 2015, 63, 203.
[2] Baron, M.; Bellemin-Laponnaz, S.; Tubaro, C.; Basato, M.; Bogialli, S.; Dolmella, A. J. Inorg.
Biochem. 2014, 141, 94.
[3] Slujter, S. N.; Elsevier, C. J. Organometallics 2014, 33, 6389.
N N
NNN
Ph
N N
NNN
PhN
NNNN
2+
Ph
AuAu
NN
NN NPh
2+
+
N N
NNN
Ph
M
Cl
NNN
RNN
2+
1) Ag2O
type A
type B
2) AuCl(SMe2)
NNN
RNN
Au Au
N
2+
1) Ag2O
N NNN
2) AuCl(SMe2)R
1) Ag2O
2) "M"
M = Au, Cu
N N
NNN
Ph
Ru
p-cym
or
ClCl
P2
53
Novel thymine-ruthenium derivatives
Silvia Bordoni1, Stefano Di Iulio1, Gilberto Pantolfi1, Stefano Cerini1, Magda
Monari2, Riccardo Tarroni3
1 Dipartimento di Chimica Industriale “Toso Montanari”, Universita’ di Bologna
Viale Risorgimento 4, 40136 Bologna, Italy, email: [email protected] 2 Dipartimento di Chimica "Giacomo Ciamician", Via Selmi 2, 40123 Bologna,
Italy
Ruthenium complexes have proved to exhibit antineoplastic activity [1,2] related to
the interaction of metal ion with DNA nucleobases. It is indeed of great interest to
provide new insights on theses cutting-edge studies such as the identification of
different coordinative modes of DNA binding sites. This report deals with the
reaction between dihydride Ruthenium complex [(PPh3)3Ru(CO)(H)2], 1, and the
Thymine Acetic Acid N[CHC(CH3)C(O)NH]CH2C(O)OH THA, as model for
nucleobases. The reaction of 1 with THA affords an unstable monohapto acetate
hydride complex, which rapidly evolves into elusive intermediates whose nature was
evidenced by NMR spectra and proposed by DFT
calculation. Crystallizations enable to freeze the species
[(PPh3)2Ru(CO)(1-THA)(2-THA)], 2, adopting
concomitant monohapto (1-O) and the chelate (2-
O,O) coordinative fashion modes. Investigations by the
analogue reactions of 1 with acetic acid confirmed the
proposed mechanism.
Further, the unexpected isolation of intermolecular
dimeric crystalline species, [Ru(CO)(PPh3)2(2-
N,O[THA(A)];1-O[THA(B)]]2, 3 whose X-ray structure,
beside the monohapto acetate coordination, shows a reciprocal interannular four-
membered (2-N,O) chelation. This fashion binding mode, displacing phosphine
ligand, enables to stabilize the less stable tautomeric form (+10.1 kcalmol-1,
calculated at B3LYP/Def2-TZVP level) of thymine. The spectroscopic features will
be presented and discussed in comparison with X-ray molecular structures and DFT
calculations.
[1] Clarke, M.J.; Sadler, P.J. Metallopharmaceuticals I:DNA Interactions.1 ed.; Springer:Dublin
1999; Vol.1, 143.
[2] Nazarov A. A.; Hartinger, C. G.; Dyson, P. J. J. Organomet. Chem. 2014, 751, 251.
[3] Rilak, A.; Bratsos, I.; Zangrando, E.; Kljun, J.; Turel, I.; Bugarčić, Ž. D.; Alessio, E. Inorg.
Chem. 2014, 53, 6113.
[4] Pettinari, R.; Marchetti, F.; Pettinari, C.; Petrini, A.; Scopelliti, R.; Clavel, C. M.; Dyson C. M. Inorg. Chem. 2014, 53, 13105.
P3
54
Synthesis of organic compounds using homogeneous catalysts
anchored on magnetic nanoparticles
Lilian M. Silva Ansaloni, Francesco Ferretti, Fabio Ragaini
Università degli Studi di Milano, Dipartimento di Chimica, via Golgi 19, Milano,
Italy, email: [email protected]
Ferrite nanoparticles have been widely studied for their interesting magnetic
properties and relatively low cost. In catalytic reactions they have been often used as
support both for heterogeneous metallic catalysts and for heterogenized
homogeneous catalysts. In fact magnetic properties allow to easily recover the
catalyst at the end of the reaction. Nanoparticles synthesis could be done with a great
number of different methods. However the use of co-precipitation method allows to
produce nanoparticles in large quantities (several grams), in a relatively short time
using mild operative condition. Ferrite nanoparticles are not very stable under
ambient conditions and unprotected show the tendency to aggregate. In this work
particle protection was performed using 10-bromodecylphosphonic acid. We then
functionalized the protecting layer with a 4-hydroxy-1-10 phenanthroline to which
palladium acetate was finally attached.
The so obtained heterogenized Pd/phenanthroline catalyst was tested in the reductive
cyclization of nitrostyrenes to indoles and in the oxidative Heck cross-coupling
reactions.
Acknowledgement: CAPES-BRAZIL Grant BEX-5963-13-3.
P4
55
Synthesis, cytotoxicity and anti-cancer activity of new alkynyl-
gold(I) complexes
Assunta De Nisi1, Vincenzo Borgia1, Christian Bergamini2, Giorgio Sartor2,
Romana Fato2, Natalia Calonghi2, Marco Bandini1, Magda Monari1
1 Department of Chemistry “G. Ciamician”, Alma Mater Studiorum, University of
Bologna, via Selmi 2, 40126 Bologna, Italy, email: [email protected] 2 Department of Pharmacy and Biotechnology, Alma Mater Studiorum, University
of Bologna, via Irnerio 48, 40126, Bologna, Italy
Nowadays, gold complexes have found a relevant position in the field of
metallodrugs due to their wide range of pharmacological activities. In fact selected
gold complexes have been employed as antimalarial agents and recently as
anticancer drugs.
The high toxicity that some gold(I), gold(III) and gold nanoparticles have shown
against several tumor cell lines inspired the development of a number of structurally
different organometallic species being the organic frameworks, constituting the
prodrug system, actively involved in determining the overall toxicity of the species.
A study, by Ott and coworkers, showed that a new family of mononuclear
alkynyl(triphenylphosphine)gold(I) complexes, and
binuclear analogues, exhibit an important
antiproliferative activity in breast adenocarcinoma and
colon carcinoma cells [1]. The propargylic sidearm
proved to contribute to the overall pharmacological
activity of this species and a modulation of this unit
could led to develop more selective and potent
candidates for anticancer drugs.
Recently a new class of alkynyl-gold(I) complexes,
carrying variously substituted propargylic amines,
have been developed and high levels of toxicity
(micromolar range) were determined for HT29,
IGROV1, HL60 and I407 cancer cell lines [2].
Encouraged by these good results the complex library
has been enlarged with the aim of finding the most active and
less toxic alkynyl-gold(I) complex.
[1] a) Fricker, S. P. Gold Bulletin 1996, 29; b) Bertrand, B.; Casini, A. Dalton Trans. 2014, 43,
4209; c) Nardon, C.; Boscutti, G.; Fregona, D. Anticancer Res. 2014, 34, 487; d) Meyer, A.;
Bagowski, C. P.; Kokoschka, M.; Stefanopoulou, M.; Alborzinia, H.; Can, S.; Vlecken, D. H.;
Sheldrick, W. S.; Wolfl, S.; Ott I. et al. Angew. Chem. 2012, 124, 9025.
[2] De Nisi, A.; Bergamini, C.; Leonzio, M.; Sartor, G.; Fato, R.; Naldi, M.; Monari, M.; Calonghi,
N.; Bandini, M. Dalton Trans. 2016, 45, 1546.
Figure: Molecular structure of compound 3ab, so far the most
active in all cell lines.
P5
56
Phosphorene, a new polydentate ligand 2D for anchoring metal
complexes
Manuel Serrano-Ruiz1, Maria Caporali1, Gabriele Manca1, Andrea Ienco1,
Francesca Telesio2, Stefan Heun2, Roberto Gobetto3, Maurizio Peruzzini1*
1 CNR-ICCOM, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy, e-mail:
[email protected] 2 NEST, Istituto Nanoscienze-CNR and Scuola Normale Superiore, Pisa, Italy
3 Università degli Studi di Torino, Dipartimento di Chimica IFM, Via P. Giuria 7,
10125 Torino, Italy
Since its discovery in January 2014 [1], Phosphorene, the new and intriguing 2D-
material formed only by P atoms, is showing fascinating electrical and optical
properties [2]. At variance with graphene, this new single layer material has free
electron pairs onto its corrugated surface that can coordinate metals ions and metal-
ligand fragments in different coordination modes (figure1). The metal-decorated
phosphorene would represent a new functionalized material with a potential catalytic
activity and unexplored electronic properties. Here, we report our preliminary results
obtained in this area describing the reactivity of exfoliated black phosphorus [3] with
metal complexes of Ru, Pt and W.
Figure 1
Acknowledgements: Thanks are expressed to EC through the European Research Council for funding the project PHOSFUN “Phosphorene functionalization: a new platform for
advanced multifunctional materials” (Grant Agreement No. 670173) through an ERC
Advanced Grant).
[1] a) Liu, H.; Neal, A.T.; Zhu, Z.; Tomanek, D.; Ye, P.D. arXiv:1401.4133v1 [cond-mat.mes-
hall]; b) Li, L.; Yu, Y.; Ye, G.J.; Ge, Q.; Ou, X.; Wu, V; Feng, D.; Chen, X.H.; Zhang, Y.
arXiv:1401.4117v1 [cond-mat.mtrl-sci].
[2] Kou, L.; Chen C.; Smith, S. C.; J. Phys. Chem. Lett. 2015, 6, 2794.
[3] Serrano-Ruiz, M.; Caporali, M.; Ienco, A.; Piazza, V.; Heun, S.; Peruzzini, M. Adv. Mater.
Interfaces 2016, 3, 1500441.
P6
57
A highly efficient Pd/CuI-catalyzed oxidative alkoxycarbonylation
of styrenes to cinnamate derivatives
Nicola Della Ca’1, Mathias Maffei1, Gabriele Giacoia1, Raffaella Mancuso2,
Bartolo Gabriele2, Elena Motti1, Mirco Costa1
1 Dipartimento di Chimica and CIRCC, Università di Parma, Parco Area delle
Scienze, 17/A, 43124 Parma, Italy, email: [email protected]
2 Dipartimento di Chimica e Tecnologie Chimiche, Università della Calabria, Via
P. Bucci 12/C, 87036 Arcavacata di Rende (CS), Italy
Carbonylation reactions represent important tools in organic chemistry allowing the
synthesis of high-value molecules, such as pharmaceuticals, agrochemicals,
cosmetic ingredients and dyes, from readily available starting materials [1]. Alkenes
and alkynes can be conveniently transformed into useful carbonylated compounds
by metal-catalyzed carbonylation processes that employ carbon monoxide as
inexpensive and easily available C1 source [2]. In this contribution a new protocol
for the alkoxycarbonylation of styrenes to the corresponding cinnamate derivatives
is described (Scheme 1). Differently substituted styrenes can be selectively
functionalized, via C-H bond activation, with formation of linear α,β-unsaturated
esters. Various palladium sources in combination with CuI have been shown to
exhibit a high catalytic efficiency using oxygen as the most cheap oxidant.
Monocarbonylated products are obtained in good yields and high chemoselectivity
working with a low CO pressure (2 bar) and an excess of air (35 bar) avoiding also
explosion risks. Commercial cinnamate derivatives can be prepared in good to
excellent yields by this very simple one-pot procedure.
Scheme 1 [1] Kollár, L. Modern Carbonylation Methods, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim, Germany, 2008.
[2] Wu, X.-F.; Neumann, H.; Beller, M. ChemSusChem 2013, 6, 229.
P7
58
Influence of metallic cations in the Wittig reaction: useful step for
the synthesis of anticancer agents
Pamela Piermattei1, Lorenzo Bisconti1, Federico Buonanno2, Simone Giorgi1,
Gabriele Lupidi1, Claudio Ortenzi2, Enrico Marcantoni1
1 School of Science and Technology, Chemistry Division, University of Camerino,
Via S. Agostino 1, 62032 Camerino, Italy, email: [email protected] 2 Laboratory of Protistology and Biology Education, Department of Education,
Cultural Heritageand Tourism, Università di Macerata, Macerata, Italy
Alkenes with a well defined geometric configuration represent an essential class of
key intermediates, and they are a continuous challenge in the synthesis of many
natural products and drugs [1]. Different methodologies have been developed, and
the Wittig reaction and related transformations for its high level of geometrical
control have become the most frequently employed [2].
The counter ion of the base used can be choose in order to obtain different
stereoselectivity in Wittig reactions [3], and in recent years, our efforts are focused
on the study of the presence of cerium for a better selectivity towards the formation
of (Z)-alkenes.
In nature (Z-)alkenes are abundant and of capital importance for their biological
activity, for this we were interested at the synthesis of hydroxyl-substituted
alkenylbenzenes because they are effective anticancer agents [4]. Typical component
of this family is the (Z)-Climacostol (1), a toxin belonging to the family of
resorcinolic lipid. It is present in prokaryotes as well as in single-celled and
multicellular eukaryotes and has attracted great attention due its antimicrobial,
cytotoxic and anticancer activities [5].
[1] Wang, J. Top. Curr. Chem. 1999, 327, 34. [2] Brien, C. J. O.; Tellez, J. L.; Nixon, Z. S.; Kang, L. J.; Carter, A. L.; Kunkel, S. R.; Przeworski,
K. C.; Chass, G. A. Angew. Che. Int. Ed. 2009, 48, 6836.
[3] Richardson, J.; Aggarwal, V. K.; Harvey, J. N. J. Am. Chem. Soc. 2006, 128, 2394.
[4] Rietjens, I. M.; Cohen, S. M.; Fukushima, S.; Gooderham, N. J.; Hecht, S.; Marnett, L. J.;
Smith, R. L.; Adams, T. B.; Bastaki, M.; Harman, C. G.; Taylor, S. V. Chem. Res. Toxicol.
2014, 27, 1092.
[5] Quassinti, L.; Ortenzi, F.; Marcantoni, E.; Ricciutelli, M.; Lupidi, G.; Ortenzi, C.; Buonanno,
F.; Bramucci, M. Chem. Biol. Interact. 2013, 206, 109.
P8
59
Non-photochemical route to tetrathiahelicenes through
Pd-mediated heteroaryl-heteroaryl bond formation
Silvia Cauteruccio1, Davide Dova1, Clara Baldoli2, Emanuela Licandro1
1 Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi 19, 20133
Milano, Italy, email: [email protected]
2 CNR-Istituto di Scienze e Tecnologie Molecolari, Via Golgi 19, 20133 Milano,
Italy
Tetrathia[7]helicenes (7-TH), formed by thiophene and benzene rings ortho-fused in
an alternating fashion, are emerging as one of the most popular class of chiral helical-
shaped molecules [1], thanks to their peculiar electronic and chiroptical properties
suitable for applications in optoelectronics [2], biology [3], and catalysis [4]. Despite
all these potential advantages, most of the synthetic methodologies to prepare 7-TH
systems involve oxidative photochemical cyclization processes, which require
specific equipment, highly diluted solutions, limiting the scale-up.
In our ongoing studies on the synthesis and functionalization of 7-TH derivatives,
we have set up an innovative and non-photochemical procedure for the synthesis of
7,8-diaryl and dialkyl substituted 7-TH compounds, exploiting a Suzuki-type cross
coupling and a Pd-catalyzed annulation with internal alkynes as key steps.
[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.; Bartoli, C.; Carrara, C.; Dova, D.; Errico, C.; Ciampi, G.; Dinucci, D.; Licandro, E.; Chiellini, F. Chem. Plus. Chem. 2015, 80, 490.
[4] Cauteruccio, S.; Dova, D.; Benaglia, M.; Genoni, A.; Orlandi, M.; Licandro, E. Eur. J. Org.
Chem. 2014, 2694.
P9
60
Switching the photochromic behavior of acenaphthylene
derivatives through an organometallic multicomponent addition
Chiara Lambruschini, Luca Banfi and Giuseppe Guanti
Department of Chemistry and Industrial Chemistry, University of Genova, Via
Dodecaneso 31, 16146 Genova, Italy, email: [email protected]
1,2-Dithienylethenes are a very promising subgroup of diarylethenes, a well-known
class of photochromic compounds [1]. These molecules undergo a photochemical
6π-electrocyclization upon UV light irradiation. The newly formed cyclic adducts
show a bathochromic shift in the UV-Vis spectrum and can be reversely opened by
visible light irradiation to restore the open form. On the contrary, cyclization is
thermally irreversible. These properties are fundamental for applications to
optoelectronic devices, such as memories and switches. To confer high fatigue
resistance, the double bond has to be tetrasubstituted and it has been demonstrated
that the optimal set-up is when the C=C bond is installed into a
perfluorocyclopentene moiety [2].
With the aim of studying other substituent we investigated the acenaphthylene
residue, in which the five membered rings are known to have a rather small aromatic
character. During our studies we discovered that simple 1,2-dithienylacenaphthylene
derivatives are not photochromic; on the other hand we found out how to favorably
switch on this behavior through an organometallic multicomponent addition.
These dihydroacenaphtylene derivatives showed photochromic property and we also
observed a different regio- and stereoselectivity depending on the nature of the
organometallic reagent.
Herein, we present the original synthesis of dihydroacenaphthylenes and the
preliminary studies of their photochromic property.
[1] a) Irie, M.; Chem. Rev. 2000, 100, 1685–1716; b) Irie, M.; Fulcaminato, T.; Matsuda, K.;
Kobatake, S. Chem. Rev. 2014, 114, 12174.
[2] Irie, M.; Lifka, T.; Kobatake, S.; Kato, N. J. Am. Chem. Soc. 2000, 122, 4871.
P10
61
Hypervalent iodine derivatives as oxidizing agents in Pd-catalyzed
reactions: an unexpected behaviour of PhI(OCOCF3)2
Tea Borelli1, Gianluigi Broggini1, Julie Oble2, Giovanni Poli2
1Dipartimento di Scienza e Alta Tecnologia, Università degli Studi dell’Insubria,
via Valleggio 9, 22100 Como, Italy, email: [email protected] 2 Sorbonne Universités, UPMC Univ Paris 06, Institut Parisien de Chimie
Moléculaire, UMR CNRS 8232, Case 229, 4 Place Jussieu 75252 Paris Cedex 05,
France
Palladium(II)-catalyzed oxidative reactions are highly efficient and synthetically
useful tools for the construction of heterocyclic scaffolds starting from easily
available non-activated olefins, allowing transformations that would be either
difficult or impossible to obtain by conventional organic chemistry[1]. For the
correct outcome of these reactions, the use of stoichiometric amount of strong
oxidizing agents is required. Among the different oxidants that have been used, the
attention was recently directed toward hypervalent iodine reagents, in particular
PhI(OAc)2, that is able to oxidize alkyl C-PdII species to deliver alkyl C-OAc, which
can then undergo further transformations. In this field, PhI(OAc)2 has been
efficiently used to promote 1,2-aminoacetoxylations of unsaturated amine
derivatives [2].
Recently, we reported the intra-intermolecular oxidative palladium-catalyzed
aminoacetoxylation of glycine allylamides as a method to access piperazinone
derivatives [3].
In the present work, we focus our attention toward the cyclization of various
aminoalkenes in the presence of different hypervalent iodine reagents. While
PhI(OAc)2 provided predictable aminopalladation/acetoxylation or
aminopalladation/dehydropalladation processes, the use of PhI(OCOCF3)2 led to
unexpected outcomes, as only allylic amination products were obtained.
These results confirm the potential of hypervalent iodine reagents as oxidants in
palladium-catalyzed reactions, and above all highlight for the first time the behaviour
of PhI(OCOCF3)2 as promoter of a direct allylic aminations.
[1] a) Beccalli, E. M.; Broggini, G.; Martinelli, M.; Sottocornola, S. Chem. Rev. 2007, 107, 5318;
b) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147.
[2] a) Liu, G.; Stahl, S. S. J. Am. Chem. Soc. 2006, 128, 7179; b) Martínez, C.; Wu, Y.; Weinstein,
A. B.; Stahl, S. S.; Liu, G.; Muñiz, K. J. Org. Chem. 2013, 78, 6309; c) Alexanian, E. J.; Lee,
C.; Sorensen, E. J. J. Am. Chem. Soc. 2005, 127, 7690; d) Rajabi, J.; Lorion, M. M.; Ly, V. L.;
Liron, F.; Oble, J.; Prestat, G.; Poli, G. Chem. Eur. J. 2014, 20, 1539.
[3] Broggini, G.; Beccalli, E. M.; Borelli, T.; Brusa, F.; Mazza, A.; Gazzola, S. Eur. J. Org. Chem.
2015, 4261.
P11
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Ru2(OAc)4Cl as catalyst in the aerobic oxidation of hydroxylamines
to nitrones
Giampiero D’Adamio1, Flavia Lupi1, Tiziano Marzo1, Francesca Cardona1, Luigi
Messori1, Andrea Goti1,2
1 Dipartimento di Chimica “Ugo Schiff”, Università degli Studi di Firenze, Via
della Lastruccia 3-13, 50019 Sesto Fiorentino (FI), Italy, email:
[email protected] 2 ICCOM-CNR, Via Madonna del Piano, 50019 Sesto Fiorentino (FI), Italy
Catalytic oxidation involving the use of oxygen (or better air) as the oxidant [1] has
attracted great interest as a clean alternative to stoichiometric or enzymatic oxidation.
Nitrones are key intermediates for the synthesis of a large number of nitrogen
containing biologically active compounds and can be obtained easily by oxidation of
the corresponding N,N-disubstituted hydroxylamines or amines [2].
In this work we employed the mixed valent complex Ru2(OAc)4Cl as transition-
metal catalyst in combination with oxygen or air for the oxidation of N,N-
disubstituted hydroxylamines to nitrones. The choice of the catalyst was made with
the purpose that the peculiar catalytic properties will be retained in
(lysozyme)Ru2(OAc)2 adduct for its possible use as an artificial metalloenzyme;
recently synthesized by some of us from direct reaction of lysozyme with the lantern
like diruthenium tetraacetate chloride under physiological conditions [3].
N,N-dibenzylhydroxylamine (1) was selected as the model substrate in order to study
the best conditions for the aerobic oxidation.
1 Mol% catalyst loading, a flux of air as oxidant, water as the solvent and heating
the reaction mixture at 50 °C were the optimal conditions. The reactivity of a series
of both aliphatic and benzylic hydroxylamines, including cyclic and enantiopure
ones, was then examined.
[1] Sheldon, R. A. Chem. Soc. Rev. 2012, 41, 1437.
[2] a) Brandi, A.; Cardona, F.; Cicchi, S.; Cordero, F. M.; Goti, A. Chem. Eur. J. 2009, 15, 7808;
b) D’Adamio, G.; Parmeggiani, C.; Goti, A.; Cardona, F. Eur. J. Org. Chem. 2015, 6541.
[3] Messori, L.; Marzo, T.; Fernandes Sanches, R. N.; Rehman, H.-R.; De Olivera Silva, D.;
Merlino, A. Angew. Chem. Int. Ed. 2014, 53, 6172.
P12
63
Assembly of the 1,5-benzodiazepine moiety via a domino gold
catalyzed hydroamination/cyclization process
Antonia Iazzetti, Sandro Cacchi, Giancarlo Fabrizi, Antonella Goggiamani
Dipartimento di Chimica e Tecnologie del Farmaco, La Sapienza, Università di
Roma, P.le A.Moro 5, 00185 Roma, Italy, email: [email protected]
The 1,5-benzodiazepine nucleus is a structural component of a vast number of
biologically active compounds exhibiting a broad spectrum of properties such as
antianxiety [1], antifungal [2], anthelmintic [2], antimicrobial [3], analgesic [4], anti-
inflammatory [4], antipyretic [4], activities. Because of this, a great deal of attention
has been dedicated to the development of synthetic routes to the construction of the
1,5-benzodiazepine skeleton, the great majority of them relying on condensation
reactions of o-phenylenediamines with a variety of carbonyl derivatives [5]. As part
of our ongoing interest in Au-catalyzed assembly of heterocyclic rings [6], we report
a process involving the use of o-phenylenediamine and propargylic alcohols 1 for
the synthesis of 1,5-benzodiazepines 2 bearing different substituents at the 2 and 4
positions (Scheme 1). Poster will cover the main features of this new synthetic
approach.
Scheme 1
[1] Kusanur, R. A.; Ghate, M.; Kulkarni, M. V. J. Chem. Sci. 2004, 116, 265.
[2] Kumar, R.; Joshi, Y. C. J. Serb. Chem. Soc. 2008, 73, 937.
[3] Singh, B.; Maheshwari, A.; Dak, G.; Sharma, K.; Talesara, G. L. Indian J. Pharm. Sci. 2010,
72, 607.
[4] Grossi, G.; Di Braccio, M.; Roma, G.; Ballabeni, V.; Tognolini, M.; Calcina, F.; Barocelli, E.
Eur. J. Med. Chem. 2002, 37, 933.
[5] Salve, P. S.; Mali, D. S. Int. J. Pharm. Bio. Sci. 2013, 4, 345.
[6] a) Ambrogio, I.; Arcadi, A.; Cacchi; S.; Fabrizi, G.; Marinelli, F. Synlett 2007, 1775; b) Cera,
G.; Piscitelli, S.; Chiarucci, M.; Fabrizi, G.; Goggiamani, A.; Ramon, R. S.; Nolan, S. P.;
Bandini, M. Angew. Chem. Int. Ed. 2012, 51, 9891; c) Arcadi, A.; Blesi, F.; Cacchi, S.; Fabrizi, G.; Goggiamani, A.; Marinelli, F. Org. Biomol. Chem. 2012, 10, 9700; d) Chiarucci, M.;
Matteucci, E.; Cera, G.; Fabrizi, G.; Bandini, M. Chem. Asian J. 2013, 8, 1776.
P13
64
Synthesis and application of a new class of cyclopentadienone iron
complexes as highly active catalysts for ketone hydrogenation
reactions
Sofia Vailati Facchini1,2, Luca Pignataro3,4, Cesare Gennari3,4, Albrecht Berkessel2,
Umberto Piarulli1
1 Università degli Studi dell’Insubria, Dipartimento di Scienza e Alta Tecnologia,
Via Valleggio 11, 22100 Como, Italy, email: [email protected] 2 Universität zu Köln, Department für Chemie, Greinstrasse 4, 50939 Köln,
Germany
3 Università degli Studi di Milano, Dipartimento di Chimica, Via C. Golgi 19,
20133 Milano, Italy
4 CNR-Istituto di Scienze e Tecnologie Molecolari (ISTM), Via C. Golgi 19, 20133
Milano, Italy
In recent years there has been a growing interest for developing efficient and
selective homogeneous iron catalysts, thanks to the far lower cost and greater
abundance of iron over the more precious metals (Pd, Rh, Ir, Ru) [1]. A very
interesting approach was presented by Knölker and co-workers with their catalyst
2a, [2] a Cp-Fe(II) hydride that can be generated in situ from the air-stable Fe(0)-
cyclopentadienone precursor 1a [3]. Catalyst 2a can promote the hydrogenation of
ketones and imines with very high efficiency (up to 3,800 TON). Based on these
premises, we have recently developed new chiral cyclopentadienone catalysts 1b,
bearing a BINOL-derived backbone, for the enantioselective hydrogenation of
ketones (up to 52% ee) [4].
Herein we disclose the synthesis, structural characterization and catalytic activity of
a new cyclopentadienone Fe-catalyst 3 which can be easily prepared in one step from
cyclooctyne. Catalyst 3 showed comparatively higher reactivity as well as excellent
selectivity for the hydrogenation of aromatic and aliphatic ketones, and great
substrate tolerance towards a wide variety of functional groups (e.g. alkynes,
halogens, aromatics, pyridines, amides, nitriles, nitro groups, cyclopropanes).
[1] Darwish, M.; Wills, M. Catal. Sci. Technol. 2012, 2, 243.
[2] Quintard, A.; Rodriguez, J. Angew. Chem. Int. Ed. 2014, 53, 4044. [3] Fleischer, S.; Zhou, S.; Junge, K.; Beller, M. Angew. Chem. Int. Ed. 2013, 52, 5120.
[4] Gajewski, P.; Renom-Carrasco, M.; Vailati Facchini, S.; Pignataro, L.; Lefort, L.; de Vries,
J.G.; Ferraccioli, R.; Piarulli, U.; Gennari, C. Eur. J. Org. Chem. 2015, 5526.
Acknowledgements: The authors thank the European Commission [ITN-EID “RE-DUCTO” PITN-GA-2012-316371] for
financial support.
P14
65
On the reactivity of redox active iron N-heterocyclic carbene
complexes.
Valerio Zanotti, Andrea Cingolani, Rita Mazzoni
Department of Industrial Chemistry “Toso Montanari”, University of Bologna,
Viale del Risorgimento 4, 40136 Bologna, Italy, email:
Redox reactions, such as hydrogenation and transfer hydrogenation, are important
processes in fine chemistry. In recent years, cyclopentadienone iron complexes have
drawn attention, in this field of chemistry, due to their air and water stability, cheap
starting materials, interesting and unique catalytic features arising from the presence
of a non-innocent ligand [1]. Herein, we report on the synthesis and reactivity of new
carbonyl iron complexes combining different ligands, such as cyclopentadienone and
variously functionalized N-heterocyclic carbene (NHC). The unique features of both
ligands are exploited to obtain new metal-ligand bifunctional catalysts to be
employed in transfer hydrogenation, as previous investigated by the research group
with Ru analogous complex [2]. Carbene coordination occurred through the
displacement of a CH3CN by transmetallation from a silver carbene intermediate to
the iron precursor, leading to the formation of the complexes shown in Figure 1 [3].
Figure 1. Dicarbonyl-cyclopentadienone-N-heterocyclic carbene iron complexes.
Although a-d complexes show low activity as catalysts for hydrogen transfer and
alcohol oxidation, studies on the reactivity of novel variously functionalized NHC
complexes, such as the photolytic behavior of the complex in Figure 2, are paving
the way for promising results in this field.
Figure 2. Photolytic promoted CO removal on neutral Fe(0) cyclopentadienone NHC complexes.
[1] Quintard, A.; Rodriguez, J. Angew. Chem. Int. Ed. 2014, 53, 4044.
[2] Cesari, C.; Cingolani, A.; Parise, C.; Zacchini, S.; Zanotti, V.; Cassani M.C.; Mazzoni, R. RSC
Adv. 2015, 5,94707.
[3] Cingolani, A.; Cesari, C.; Zacchini, S.; Zanotti, V.; Cassani, M.C.; Mazzoni, R. Dalton Trans.
2015, 44, 94707.
P15
66
Palladium catalyzed reductive cyclization of nitroolefins: a
powerful tool for the synthesis of indoles, pyrroles and
thienopyrroles
Fabio Ragaini1, Mohamed A. EL-Atawy1,2, Francesco Ferretti1
1 Università degli Studi di Milano, Dipartimento di Chimica, via C. Golgi 19,
20133 Milano, Italy, email: [email protected] 2 Department of Chemistry, Faculty of Science, Alexandria University, P.O 426
Ibrahimia, 21321 Alexandria, Egypt
Nitroolefins are widely used intermediates in synthetic organic chemistry. Owing to
our interest in the development of transition metal catalyzed synthesis of nitrogen
heterocycles, we recently studied the reductive cyclization of -nitrostyrenes to
indoles [1] (scheme 1).
Scheme 1
With the purpose to test our system in the synthesis of other heterocyclic systems,
we applied the reaction to the preparation of thienopyrrole from (2-
nitrovinyl)thiophenes (scheme 2) and of pyrroles from nitrodienes (scheme 3).
Scheme 2
Scheme 3
The strength of this reaction with respect to many reported cyclization reaction
affording fused bicyclic heterocycles, is that it does not require the use of a doubly
functionalized arene (e.g. an o-bromoaniline) and in most cases the starting materials
can be easily prepared by a Henry reaction. In the case of the synthesis of pyrroles
the preparation of the starting material can be designed in order to obtain mono, di-
and trisubstituted derivatives.
[1] Ferretti, F.; El-Atawy, M. A.; Muto, S.; Hagar, M.; Gallo, E.; Ragaini, F. Eur. J. Org. Chem.
2015, 5712.
P16
67
Bridging coordination chemistry and heterogeneous catalysis:
Co/BIAN complexes as precursors for nitroarene hydrogenation
catalysts
Dario Formenti1,2, Francesco Ferretti1, Christoph Topf2,3, Annette-Enrica Surkus2,
Kathrin Junge2, Matthias Beller2, Fabio Ragaini2
1 Dipartimento di Chimica, Università degli Studi di Milano, Via C. Golgi 19,
20133 Milano, Italy, email: [email protected] 2 Leibniz Institut für Katalyse e.V., Albert-Einstein Strasse 29a, 18059 Rostock,
Germany 3 Institut für Katalyse, Johannes Kepler Universität Linz, Altenbergerstrasse 69,
4040 Linz, Austria
Transition-metal based nitrogen-doped modified carbon composites are attractive
tools in the catalysis field. Their unique electronic, chemical and physic properties
permit the preparation of active and recyclable catalysts whose applications span
organic synthesis, pollutants remediation, electrocatalysis and energy-related
transformations. An efficient way to synthetize them involves the pyrolysis of well-
defined metal complexes immobilized on various supports. In this study, we present
the preparation, characterization and application of seven different Co-based
catalysts in which the nitrogen network is provided by the pyrolysis of Co/BIAN
complexes supported on Vulcan carbon. These materials show a core-shell
architecture that allows achieving excellent selectivities in the hydrogenation of
various substituted nitroaromatics. Straightforward kinetic experiments allowed us
to correlate the catalytic activity with the amount and type of nitrogen (determined
by CHN and XPS analyses) present in the materials. Finally, based on the whole
collected data, a reaction mechanism that involves a heterolytic activation of the
dihydrogen molecule was postulated.
[1] Formenti, D.; Ferretti, F.; Topf, C.; Surkus, A.-E.; Pohl, M.-M.; Junge, K.; Beller, M.; Ragaini,
F. submitted.
P17
68
Synthesis and characterization of new carbamates of early
transition metals in high oxidation state
Giulio Bresciani1, Fabio Marchetti1, Guido Pampaloni1, Stefano Zacchini2
1 Dipartimento di Chimica e Chimica Industriale, University of Pisa, Via G.
Moruzzi 13, 56124 Pisa, Italy, email: [email protected]
2 Dipartimento di Chimica Industriale “Toso Montanari, University of Bologna,
Viale Risorgimento 4, 40136 Bologna, Italy
N,N-dialkylcarbamates are monoanionic oxygen donors of formula [O2CNR2]R =
H, alkyl or aryl). Homoleptic N,N-dialkylcarbamates of group 4 and group 5 metals
may act as catalytic precursors for polymerization reactions [1], and the mixed
chlorocarbamate TiCl2(O2CNMe2)2 exhibited superior activity in propylene
polymerization [2]. In this context, despite group 4 and group 5 metal fluorides (or
their simple derivatives) have recently found application as effective catalytic
precursors for a variety of organic transformations [3], examples of mixed
fluorocarbamates have not been reported hitherto.
Herein, we describe different synthetic strategies for the preparation of a variety of
mixed chloro- and fluoro-carbamates of high valent metals belonging to groups 4-6
(Figure 1). The new compounds have been characterized by elemental analysis, IR
and NMR spectroscopy and, in some cases, by single crystal X-ray diffraction.
Figure . Synthesis of Niobium(V) fluorocarbamates
[1] a) Marchetti, F.; Pampaloni, G.; Pinzino, C.; Renili, F.; Repo, T.; Vuorinen, S. Dalton Trans.
2013, 42, 2792; b) Raspolli Galletti, A. M.; Pampaloni, G. Coord. Chem. Rev. 2010, 254, 525.
[2] Marchetti, F.; Pampaloni, G.; Patil, Y.; Raspolli Galletti, A. M.; Renili, F.; Zacchini, S.
Organometallics 2011, 30, 1682.
[3] a) Coman, S. M.; Verziu, M.; Tirsoaga, A.; Jurca, B.; Teodorescu, C.; Kuncser, V.; Parvulescu,
V. I.; Scholz, G.; Kemnitz, E. ACS Catal. 2015, 5, 3013; b) Yoshiki, M.; Ishibashi, R.; Yamada, Y.; Hanamoto, V. Org. Lett. 2014, 16, 5509; c) Soo Kim, S.; Rajagopal, G.; George,
S. C. Appl. Organomet. Chem. 2007, 21, 368.
P18
69
New experimental and theoretical study on nitriles bonded to Pt(II)
centers
Paolo Sgarbossa1, Alberto Albinati2, Roberta Bertani1, Maurizio Casarin3,
Girolamo Casella4, Giulia Mangione3, Mirto Mozzon1, Silvia Rizzato2, Sergio
Tamburini5, Alfonso Venzo3
1 Dipartimento di Ingegneria Industriale, Università di Padova, via Marzolo 9,
35131 Padova, Italy, email: [email protected] 2 Dipartimento di Chimica, Università di Milano, via Golgi 19, 20133 Milano, Italy
3 Dipartimento di Scienze Chimiche, Università di Padova, via F. Marzolo 1,
35131, Padova, Italy 4 Dipartimento di Scienze della Terra e del Mare; Università degli Studi di
Palermo, Via Archirafi 20, 90123, Palermo, Italy 5 National Research Council of Italy (CNR), Institute for Energetics and
Interphases (IENI), Corso Stati Uniti 4, 35127 Padova, Italy
Cis- and trans-[PtCl2(NCR)2] (R = Me, Ph, Bz) have been widely used as starting
compounds in the synthesis of a range of Pt(II) complexes through both substitution
of the nitrile ligands or reaction with suitable nucleophiles [1]. Herein we report a
new study on the properties of nitrile to Pt(II) bonding by updating their
spectroscopic characterization data both in solution and in the solid state and
redetermining the X-ray structures of cis-[PtCl2(NCMe)2], cis- and trans-
[PtCl2(NCPh)2] at low temperature.
FT-IR blue-shift of the
CN bond and 13C NMR
chemical shift shielding
were observed when
comparing the
coordinated nitrile to
the free ones. Finally,
DFT level
computational studies,
showed that the
increased reactivity of the coordinated nitriles could be explained by the energy
decreasing of the ligand LUMOs, in agreement with the orbital control model
previously proposed for trans-[PtCl2(NCMe)2] [2-3].
[1] Michelin, R. A.; Mozzon, M.; Bertani, R. Coord. Chem. Rev. 1996, 147, 299.
[2] Kuznetsov, M. L.; Bokach, N. A.; Kukushkin, V. Y.; Dement’ev, A. I. Russ. J. General Chem.
2009, 79, 232.
[3] Kuznetsov, M. L.; Bokach, N. A.; Kharlampidi, D. D.; Medvedev, Y. N.; Kukushkin, V. Y.;
Dement’ev, A. I. Russ. J. General Chem. 2010, 80, 458.
P19
70
Ullmann coupling catalyzed by gold nanoparticles supported on
silicon nanowires
M. Casiello1, W. Sikorski3, P. Cotugno1, A. Monopoli1, F. Ciminale1, R. Picca1, N.
Cioffi1, L. Bellebuono1, A. Irrera4, S. Trusso4, M. J. Lo Faro4, A. M. Trzeciak3, A.
Nacci1,2
1 Department of Chemistry, University of Bari “Aldo Moro”, Via Orabona 4, 70126
Bari, Italy, email: [email protected] 2 CNR – ICCOM, Department of Chemistry, University of Bari “Aldo Moro”, Via
Orabona 4, 70126 Bari, Italy
3 University of Wrocław, Faculty of Chemistry, 14 F. Joliot-Curie 50-383 Wrocław,
Poland
4 CNR IPCF, Viale Ferdinando Stagno D’Alcontres 37, 98158, Messina, Italy
In recent decades gold catalysis has gained great attention from the scientific
community. To date, a number of homogeneous gold(I) and gold(III) catalysts
display high efficiency in promoting several unique chemical transformations [1].
Moreover, gold is equally effective as heterogeneous catalyst, especially when it is
subdivided down to nanoscale. Recently, some of us proposed an Ullmann-type
homocoupling in water of aryl halides catalyzed by free gold(0) nanoparticles
prepared in situ by reduction of HAuCl4 with glucose and stabilized by
tetrabutylammonium salts [2]. Unfortunately, recovery of catalyst was prohibitive.
Among the variety of supports for heterogeneous catalysis, silicon has recently
gained great interest, especially when structured as nanowires that can ensure an high
surface development and a better contact with the reaction solution [3]. Moreover,
the wafer form of silicon support would permit to recover nanocatalyst by simple
removal and washing avoiding tedious separation techniques like filtration or
centrifugation that can lead to the loss of material. In this communication we report
the use of a gold(0) nanoparticles catalyst supported on
silicon nanowires (Au@SiNW), prepared by metal assisted chemical etching and
decorated by pulsed laser ablation, in an Ullmann-type homocoupling of aryl halides
carried out in water.
[1] Corma, A.; Leyva-Pérez, A.; Sabater, M. J. Chem. Rev. 2011, 111, 1657.
[2] Monopoli, A.; Cotugno, P.; Palazzo, G.; Ditaranto, N.; Mariano, B.; Cioffi, N.; Ciminale, F.;
Nacci, A. Adv. Synth. & Catal. 2012, 354, 2777.
[3] Yamada, Y. M. A.; Yuyama, Y.; Sato, T.; Fujikawa, S.; Uozumi, Y. Angew. Chem. 2014, 126,
131.
P20
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Auto-tandem catalysis in ionic liquids: palladium – iodide
catalyzed recyclable synthesis of 2-Oxazolidinones
Raffaella Mancuso, Asif Maner, Ida Ziccarelli, Bartolo Gabriele
Dipartimento di Chimiche e Tecnologie Chimiche, Università della Calabria,
87036 Arcavacata di Rende, Cosenza, Italy, email: [email protected]
2-Oxazolidinones are a very important class of heterocyclic compounds. Chiral 2-
oxazolidinones are widely used as chiral auxiliaries in many important asymmetric
syntheses. Moreover, oxazolidinone derivatives have shown important
pharmacological properties, in particular as antibacterial agents.
The importance of these heterocyclic derivatives justifies the continuous efforts for
developing novel approaches to their synthesis. A particularly attractive route to the
formation of the 2-oxazolidinone core is based on annulation of a suitable acyclic
precursor, which can allow the regioselective preparation of the final heterocycle
with the desired substitution pattern [1].
We have found that 2-oxazolidinones 3 can be conveniently synthesized in good
yields (70-85%) through the concatenation of two catalytic cycles, both promoted by
PdI2, corresponding to oxidative aminocarbonylation of the triple bond of 2-
ynylamines 1 with dialkylamines 2 followed by cyclocarbonylation, in an ionic
liquid as the solvent (BmimBF4), according to Equation 1.
R3
R2
H2O
PdI2/KI
BmimBF41
3
2
+ 2 CO + R2NH + O2N O
R1
R2 CHCNR2
O
(1)R1HN
O
Reactions are carried out at 100 °C in the presence of catalytic amounts of PdI2 in
conjunction with KI and H2O, in BmimBF4, as the solvent, and under 40 atm of a
4:1 mixture of CO/air for 24 h. The solvent-catalyst system can be conveniently
recycled several times without appreciable loss of activity.
[1] Gabriele, B.; Plastina, P.; Salerno, G.; Mancuso, R.; Costa, M; Org. Lett. 2007, 9, 3319.
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Synthesis of large ring size nitrogen containing heterocycles
via ring closing ene-yne metathesis
Andrea Penoni, Erik Berti, Giovanni Palmisano
Dipartimento di Scienza e Alta Tecnologia, Università degli Studi dell’Insubria,
via Valleggio 9, 22100 Como, Italy, email: [email protected]
Reactions with high atom economy are of primary importance in modern organic
chemistry. In this field, polyunsaturated substrates have led to the discovery of a
number of unprecedented transformations in the presence of transition-metal
catalysts.
Among available atom-economic transformations, metathesis reactions remain
exclusive because of the increased molecular complexity achieved in one chemical
step. Olefin and ene-yne metathesis were introduced respectively by Calderon [1]
and Katz [2] and attracted enormous attention due to their potential generation of a
wide number of carbocyclic and heterocyclic structures. In 2005 Chauvin, Grubbs
and Schrock were awarded with the Nobel Prize in Chemistry [3] “for the
development of the metathesis method in organic synthesis”. Novel regioselective
ring closing ene-yne metathesis provided an efficient access to different substituted
1-benzazepine scaffolds. The reported synthetic approach could also be used as a
powerful tool for the selective formation of a highly functionalizable 2-benzazepine
core. This synthetic protocol was even proved to be an efficient way to afford a
functionalizable benzazocine derivative. Our recent developments involve the
synthetic approach to 9- to 12-membered ring nitrogen-containing heterocycles.
[1] Calderon, N.; Chen, H. Y.; Scott, K. W. Tetrahedron Lett. 1967, 8, 3327.
[2] Katz, T. J.; Sivavec, T. M. J. Am. Chem. Soc. 1985, 107, 737.
[3] For Nobel Prize announcement, see: Angew. Chem. Int. Ed. 2005, 44, 6982.
P22
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Coupling isocyanide-based multicomponent reactions with two
sequential metal catalysed cyclizations: a fast track to polycyclic
alkaloid-like structures
Luca Banfi, Andrea Basso, Lisa Moni, Marco Piccardo, Renata Riva, Martina
Spallarossa
Department of Chemistry and Industrial Chemistry, University of Genova, via
Dodecaneso 31, 16146 Genova, Italy, email: [email protected]
The Passerini and Ugi multicomponent reactions, when followed by post-MCR
cyclizations, have been demonstrated to be very useful in the diversity-oriented
(combinatorial) assembly of heterocycles. In this work we have exploited an original
protocol where these two isocyanide-based MCRs are followed by two sequential
organometal catalysed reactions affording complex polycyclic systems that resemble
the structure of natural alkaloids. As the first step we have employed a quite efficient
Tsuji-Trost (TT) allylation of the NH group of the isocyanide-derived secondary
amide [1]. As the second cyclization, which takes advantage of the terminal C=C
bond generated by TT, we have studied, so far, a ring-closing metathesis (RCM) and
a Heck reaction. The former has been quite successful, whereas the latter has led to
poorer yields due to side-reactions that will be discussed in the poster. The
implementation of the methodology required the synthesis of appropriate starting
components: a) benzaldehydes bearing an allyl carbonate at the ortho positions (for
both approaches); b) isocyanides containing a terminal double bond (for the RCM
approach); c) ortho-iodo aryl isocyanides (for the Heck approach).
The MCR-TT-RCM three step sequence has been demonstrated to have a wide
applicability and a small library of compounds, differentiated both at the decorations
(substituents), and at the scaffold level, has been prepared.
[1] Riva, R.; Banfi, L.; Basso, A.; Cerulli, V.; Guanti, G.; Pani, M. J. Org. Chem. 2010, 75, 5134.
P23
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Design and synthesis of photosensitizers with alkoxysilane
anchoring groups for new generation solar cells
Matteo Bessi1,2, Marco Monini2, Massimo Calamante2,3, Alessandro Mordini2,3,
Adalgisa Sinicropi1,2, Mariangela Di Donato3,4, Alessandro Iagatti3,4, Paolo
Foggi3,4, Lorenzo Zani2, Gianna Reginato2
1 Dipartimento di Biotecnologie, Chimica e Farmacia, Università degli Studi di
Siena, Via A. Moro 2, 53100 Siena, Italy, e-mail: [email protected] 2 Istituto di Chimica dei Composti Organometallici (CNR-ICCOM), Via Madonna
del Piano 10, 50019 Sesto Fiorentino, Italy
3 Dipartimento di Chimica ‘‘U. Schiff’’, Università degli Studi di Firenze, Via della
Lastruccia 13, 50019 Sesto Fiorentino, Italy
4 European Laboratory for Non Linear Spectroscopy (LENS), Università degli
Studi di Firenze, Via Nello Carrara 1, 50019 Sesto Fiorentino, Italy
Dye-sensitized solar cells (DSSC) have been the subject of constant attention in
recent years thanks to the enhancement in their efficiency and stability [1]. Metal-
free D-π-A dyes are especially interesting, since their particular architecture allows
a fine adjustment of their photo- and electrochemical properties [2].
First, we modified the structure of already known dye DF15 by introducing two
alkoxysilane (recently awarded to be one of the most stable and high-performing
anchoring units for DSSC [3]) by employing a Pd-catalyzed silylation reaction.
Then, we altered the dye conjugate unit by replacing the central thiophene ring with
a more electronrich ProDOT moiety, keeping the trialkoxyphenylsilyl anchor, with
the aim to improve the dye light harvesting properties. The corresponding
cyanoacrylic acid dye was also prepared for comparison
Finally, we analyzed the interfacial charge transfer processes taking place between
the dyes and a nanocrystalline semiconductor (TiO2), by means of UV-Vis and IR
transient absorption spectroscopy. The results obtained with the various anchoring
groups were compared in order to study the different dynamics occurring in each
case.
[1] Hagfeldt, A.; Boschloo, G.; Sun, L.; Kloo, L.; Pettersson, H. Chem. Rev. 2010, 110, 6595.
[2] Ooyama, Y.; Harima, Y. ChemPhysChem. 2012, 13, 4032.
[3] Kakiage, K.; Aoyama, Y.; Yano, T.; Otsuka, T.; Kyomen, T.; Unno, M.; Hanaya, M. Chem. Commun. 2014, 50, 6379.
P24
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Rapid one-pot synthesis of heterocycles by sequentially palladium-
catalysed one-pot processes
Alissa C. Götzinger, Corinna Hoppe, Thomas J. J. Müller
1 Heinrich Heine Universität, Universitätsstraße 1, 40225 Düsseldorf, Germany,
email: [email protected]
Unsymmetric alkynes are valuable building blocks in heterocycle synthesis that can
also exhibit interesting properties for applications in molecular electronics. The most
common approach to this substance class requires three steps, proceeding via the
Sonogashira reaction of an aryl halide with trimethylsilyl acetylene, followed by
deprotection and coupling with a second aryl halide or aroyl chloride [1].
We herein present a protecting-group free, sequentially palladium-catalysed three
component approach to diarylalkynes and alkynones. Terminal alkynes are generated
in situ by palladium-catalysed coupling of aryl iodides with ethynyl magnesium
bromide [2], followed by Sonogashira coupling with no further addition of palladium
catalyst. The modular nature of the reaction, readily available starting materials, mild
reaction conditions, and short reaction times allow for the quick and convenient
synthesis of a large variety of target molecules [3].
The sequence can be extended by cyclocondensation of the alkynones intermediates
with dinucleophiles. A three step, four component one-pot syntheses of pyrazole [4]
and pyrimidine [5] derivatives was successfully established using hydrazine
derivatives and benzamidinium salts, respectively.
In summary, we disclose a convenient and versatile sequentially palladium-catalysed
strategy for the synthesis of unsymmetric alkynes and heterocycles. The reaction
proceeds with a large variety of substrates and can be modified and extended to give
access to different target molecules. No protecting groups are necessary and all
reactants and catalysts are readily available and easy to handle.
[1] Chinchilla, R.; Nájera, C. Chem. Rev. 2007, 107, 874.
[2] Negishi, E.-i.; Kotora, M.; Xu, C. J. Org. Chem. 1997, 62, 8957.
[3] Götzinger, A. C.; Müller, T. J. J. Org. Biomol. Chem. 2016, in press.
[4] Willy, B.; Müller, T. J. J. Eur. J. Org. Chem. 2008, 24, 4157.
[5] a) Karpov, A. S.; Müller, T. J. J. Synthesis 2003, 2815; b) Boersch, C.; Merkul, E.; Müller, T.
J. J. Angew. Chem., Int. Ed. 2011, 50, 10448.
P25
76
Anti-inflammatory and cytoprotective effects of faah-cox inhibition
Marco Migliore1, Rita Scarpelli1, Oscar Sasso1, Damien Habrant1, Clara Albani1,
Glauco Tarozzo1, Sine Mandrup Bertozzi1, Maria Summa1, Andrea Armirotti1,
Guillermo Moreno-Sanz2, Daniele Piomelli1,2
1 Drug Discovery and Development, Fondazione Istituto Italiano di Tecnologia, via
Morego 30, I-16163 Genova, Italy, email: [email protected] 2 Departments of Anatomy and Neurobiology, Pharmacology and Biological
Chemistry, University of California, Irvine, USA, 92697-4621.
Our recent findings describe the first class of systemically active agents that
simultaneously inhibit FAAH, COX-1, and COX-2 with high potency and selectivity
[1,2]. The class prototype, ARN2508 is a potent and selective FAAH, COX-1, and
COX-2 inhibitor (FAAH IC50 = 31 nM, COX-1 IC50 = 12 nM, and COX-2 IC50 =
430 nM). After oral administration in mice, ARN2508 engages its intended targets
and exerts profound therapeutic effects in models of intestinal inflammation, without
any overt signs of gastric toxicity. These results demonstrate that, unlike nonsteroidal
anti-inflammatory drugs (NSAIDs), ARN2508 indeed protects the GI track from
NSAID-induced damage through a mechanism that requires FAAH inhibition.
Herein, our current progress in the lead optimization of ARN2508 will be presented.
These results open the possibility for future investigations of the potential therapeutic
applications of the FAAH/COX blockage in other pathological conditions in which
FAAH and COX are higher expressed, including chronic inflammation and
neurodegenerative disorders.
[1] Migliore, M.; Habrant, D.; Sasso, S.; Albani, C.; Mandrup Bertozzi, S.; Armirotti, A.; Piomelli,
D.; Scarpelli, R. Eur. J. Med. Chem. 2015, 109, 216.
[2] Sasso, O.; Migliore, M.; Habrant, D.; Armirotti, A.; Albani, C.; Summa, M.; Moreno-Sanz, G.;
Scarpelli, R.; Piomelli, D. FASEB J. 2015, 29, 2616.
P26
77
Synthesis of intensively blue 3-hydroxyisoquinolines through a
sequential Ugi four-component reaction/reductive Heck cyclization
Lisa Moni1, Melanie Denißen2, Gianluca Valentini1, Thomas J. J. Müller2, Renata
Riva1 1 Dipartimento di Chimica e Chimica Industriale, Università di Genova, Via
Dodecaneso 31, 16146 Genova, Italy, email: [email protected] 2 Institut für Organische Chemie und Makromolekulare Chemie, Heinrich Heine
Universität Düsseldorf, D-40225 Düsseldorf, Germany
A convergent and fast approach to the synthesis of highly functionalized 3-
hydroxyisoquinolines, either as a one-pot or a two step sequence, is reported. The
key steps are an Ugi multicomponent reaction and a subsequent intramolecular
reductive Heck reaction. 3-Hydroxyisoquinolines are rather unexplored compounds
having nevertheless an interesting biological activity [1]. Moreover, scaffold 1
displays very interesting photophysical properties as blue-fluorescence emitter,
which makes its application in the field of material sciences very attractive. For this
reason, photophysical studies on the absorption and static fluorescence, the influence
of substitutions and the protonation on the luminescent properties were performed
[2].
[1] Kanojia, R. M.; Press, J. B.; Lever, O. W.; Williams, L.; McNally, J. J.; Tobia, A. J.; Falotico,
R.; Moore, J. B. J. Med. Chem. 1988, 31, 1363. [2] Moni, L.; Denißen, M.; Valentini, G.; Müller, T. J. J.; Riva, R. Chem. Eur. J. 2015, 21, 753.
P27
78
Palladium mesogens “rod-like”: synthesis and properties
Gabriele Colombo Castelli, Edoardo Cesarotti
University of Milan, Via Venezian 21, 20133 Milano, Italy, email:
Protagonist of the work is the organopalladium material chemistry and the actors are
the liquid crystals. Synthesis of suitable Schiff bases, which present liquid crystalline
character, allows the orthometallation with palladium acetate, to give dimeric
compounds. It is easy to operate with substitution reactions, imputing the
halogenated bridges in place of acetate bridges between the Schift bases-ligands.
After that, another reaction produces a monomeric complex: especially the
fluorurated complex with chiral chain shows surprising properties as a strong
nematic phase.
All complex with chiral chain present a lower melting point and a disordered liquid
crystalline phase, the cholesteric phase or the C* phase, interesting from the
applications point of view. The analysis is done by the use of DSC in order to
understand the behavior of the liquid crystal while the microscopy is essential to
characterize the liquid crystal phase.
[1] Artigas, Mol. Cryst. Liq. Cryst. 1985, 130, 337.
[2] Ghedini M. Inorganica Chimica Acta 2000, 308, 121.
[3] Espinet, Organometallics 1990, 9, 555.
[4] Hussain, I. Eur. J. Chem. 2008, 503.
[5] Mahima Goel, B. J. Phys. Chem. 2010, 114, 12508.
P28
79
A new powerful, small footprint reactor, the Phoenix reactor
(ThalesNano), allows researchers to explore new chemical
processing windows in continuous flow
Stefano Giovanninetti, Federico Squassabia
Stepbio s.r.l. via Paolo Nanni Costa 12/3/L, 40133 Bologna, Italy, email:
[email protected], [email protected]
The importance of developing solvent free reaction, without the need for further
downstream processing, is highlighted in the Claisen rearrangement and subsequent
reduction presented by Dr. Claudio Battilocchio and Prof. Steven V. Ley from the
Innovative Technology Centre, Department of Chemistry, University of Cambridge.
In this work, solvent-free reactions are carried out using the Phoenix reactor, a small
footprint reactor designed for high-temperature and high-pressure continuous
processes, in order to achieve high productivity and ultimately intensify the process.
P29a
80
MEthane activation via integrated MEmbrane REactors
(MEMERE)
Valentina Cinti, Marco Molica Colella
CiaoTech PNO Group, Via Pacini 11, 20144 Milano, Italy, e-mail:
[email protected]; [email protected]
The MEMERE project responds to the EU Horizon 2020 call SPIRE-05-2015 and is a research and innovation project aiming at methane activation towards C2+, funded under the Grant Agreement n. 679933. The focus of the project is air separation through novel MIEC membranes integrated within a
catalytic reactor operated at high temperature for OCM allowing integration of different process steps in a single multifunctional unit and achieving significantly higher yields in comparison with the conventional reactor technologies, combined with improved energy efficiency. MEMERE will develop new O2 selective (supported) membranes for high temperature air separation and integrate these membranes in a novel membrane reactor for direct conversion of methane to C2. This high temperature membrane reactor module will have an immediate result on the significantly increased C2 yields because of the distributive oxygen feeding and improved temperature control of the reactor, combined with improved overall plant efficiency and costs, because a costly cryogenic air separation unit required in competing technologies is avoided, while downstream separation units will be simplified/reduced in volume or operating costs. This new concept will thus combine the advantages of both high temperature membranes and membrane reactors resulting in a breakthrough technology in the field of methane activation to ethylene. The great advantages of the novel membrane reactor are also accompanied by challenges that the MEMERE consortium will tackle via a combination of detailed experimentation and testing to generate feedback to the materials producers. In particular, the development and testing of novel oxygen transport membranes for application under reactive (reducing) OCM conditions. The MEMERE process can also be extended to other partial oxidation processes such as methane autothermal reforming as the challenges of the process and advantages of the novel approach are similar.
The MEMERE consortium covers the whole value-chain. It brings together multidisciplinary expertise of material development (powder, catalyst and membranes), chemical and process engineering, modelling (from thermodynamics to unit operation modelling to system integration), membranes modules and reactors development, LCA and industrial study, innovation management
and exploitation. The consortium gathers 11 partners, being 7 industrial partners and among these 5 SMEs, including Switzerland among the represented countries. MEMERE will work over 4 years, with an overall budget of 5.745.110€ and an EC grant related of 5.428.860€. It is worth noting that personnel costs are 3.375.077€ (59%). These costs are directly related to the persons/month calculation, which amounts to around 538 over 4 years: 35% of the person months is dedicated to PhD students.
P29b
81
The Indus3Es Project: New technologies for utilization of heat
recovery in large industrial systems
Valentina Cinti, Patrizia Circelli
CiaoTech PNO Group, Via Pacini 11, 20144 Milano, Italy , e-mail:
[email protected]; [email protected]
The Indus3Es project, received funding under H2020-EE-18-2015:
New technologies for utilization of heat recovery in large industrial
systems, considering the whole energy cycle from heat production to
transformation, delivery and end use. Funded under the Grant
Agreement 680738, the main objective of the project is to develop an
economically viable solution for industry, appropriate for existing
plants and adaptable to various industrial processes. The developed system will
be demonstrated in real environment in Tüpras, the main petrochemical industry
in Turkey, enabling to analyze besides integration aspects, operational and
business issues. Indus3Es System will be defined and optimized for different
specificities in different sectors and industrial processes, for which up-scaling of the
demonstrated technology and replication studies will be performed.
Indus3Es system will have a relevant impact making possible an energy
efficiency increase and reduction of primary energy consumption
of most energetic intensive industries in Europe.
The embodied energy, the environmental footprint of the
products and the manufacturing costs of energy intensive
industries will be reduced, increasing the competitiveness of
European products. Moreover, it will allow a sustainable economic
activity for local “auxiliary” companies, usually SMEs, in high added value
services related to the energy efficiency measures for industry. Studies will be
carried out through the project to maximize the future commercialization and
exploitation of the developed technology and system. During the project the AHT technology will be demonstrated in a real environment,
under working conditions of a Tüpras’ refinery.
The consortium of the Indus3Es Project consists of 10 partners: 4 Research
Organisations (TECNALIA, TU Berlin, CIRCE and Technion),
3 SMEs (Bs Nova, Aiguasol and PNO) and 3 large industries
(Tupras, Repsol and Fertinagro). The Research organisations in
charge of the main fundamental research activities related to the
envisaged developments are highly experienced on absorption technology and heat
transformers systems; the companies will bring the business spirit and industrial
knowledge, while the large companies will be key to ensure a successful
demonstration and replication of the project results. TECNALIA , one of the main
Research & Technology Organizations (RTO) in Europe, is the Coordinator of
the project.
P29c
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REE4EU: integrated high temperature electrolysis (HTE) and Ion
Liquid Extraction (ILE) for a strong and independent European
Rare Earth Elements Supply Chain Valentina Cinti, Patrizia Circelli
CiaoTech PNO Group, Via Pacini 11, 20144 Milano, Italy, e-mail: [email protected]
The REE4EU project, funded in the frame of Horizon 2020 TOPIC
SPIRE-07-2015 under Grant Agreement n° 680507, will realize a
breakthrough innovation in the field of recovery technologies for metals
and other minerals. REEs are considered “key-enablers” of green technologies, as
they are used in hybrid electric vehicles, wind mills, and highly efficient electric
motors. The dependence on Chinese exports makes Europe, and western countries in
general, extremely dependent and vulnerable to Chinese market control. Therefore REE are
considered to be materials with the highest supply-risk. Regaining REE from RE-containing waste
streams may constitute an important RE secondary source in Europe. A recent study, based on detailed
trade data, estimates the global trade in RE-containing products in 2010 at around €1.5 trillion, or
13% of the global trade. However, only 1% of RE waste is being recovered as no adequate process is
currently available.
REE4EU will open-up a fully new route bringing recovery of in-process wastes
from PM manufacturing within reach. The REE4EU project will develop, validate
and demonstrate in 2 industrially relevant Pilots an innovative Rare Earth Alloys
(REA) production route from permanent magnets PM and Ni metal hydride (NiMH)
Battery waste. The targeted integrated solution is based on recently developed lab-
proven technologies for direct high temperature electrolysis of REA production. It
will be combined in the pilots with an innovative and proven Ionic Liquid Extraction or tailored
hydrometallurgical pre-treatment to demonstrate dramatic improvements in cost and
environmental performance compared to state of the art technologies.
The project involves in its consortium 14 partners from 7 European Countries representing the
full value chain including (SME and large) RE metal producers, PM manufacturer, SME process
engineering companies and LCA experts, large electronics and battery recycling companies (LCM,
VAC, ELKEM, IDENER, A3I-INOVERTIS, SNAM, STENA), SME technology transfer, innovation
specialists as well as chemical and end-user associations (PNO, CEFIC and AVERE). Together with
4 top research institutes (SINTEF the coordinator, TECNALIA, UPS’ LABORATOIRE DE GÉNIE
and CEA) on high temperature electrolysis, ionic liquids and RE recycling the REE4EU consortium
will prove technical and economic viability on in-process PM waste (swarf), as well as end-of-life
(EoL) PM and NiMH battery waste, develop urgently required market data on EoL RE availability
and a triple value-chain business case for a new European Rare Earth Alloys (REA) production sector
from secondary raw material.
The project will prove technical and economic viability on in-process permanent magnet waste,
as well as end-of-life permanent magnets and NiMH battery waste. The targeted integrated
solution will demonstrate dramatic improvements in cost and environmental performance compared
to state of the art technologies. This includes avoidance of process steps, 50% energy savings, and
100% recycling of reagents as opposed to disposal of strong acid leaching agents in state of the art
pre-treatment steps. REE4EU will also develop urgently required market data on EoL RE availability
and a triple value-chain business case for a new European secondary rare earth alloys production
sector. This will create new jobs, increase Europe’s independence from imports and last but not least,
provide valuable raw materials for fast growing European green-technology industries such as
electrical/hybrid vehicles and wind turbines.
83
List of Participants
Albinati Alberto [email protected]
Anselmo Manuel [email protected]
Banfi Luca [email protected]
Baron Marco [email protected]
Basso Andrea [email protected]
Bessi Matteo [email protected]
Bordoni Silvia [email protected]
Borelli Tea [email protected]
Brenna Stefano [email protected]
Bresciani Giulio [email protected]
Capacci Chiara [email protected]
Capriati Vito [email protected]
Cardona Francesca [email protected]
Caselli Alessandro [email protected]
Casiello Michele [email protected]
Cauteruccio Silvia [email protected]
Cevasco Giorgio [email protected]
Cimino Alessandro [email protected]
Cinti Valentina [email protected]
Colombo Castelli Gabriele [email protected]
Conte Valeria [email protected]
D'Adamio Giampiero [email protected]
De Nisi Assunta [email protected]
84
Della Ca Nicola [email protected]
Dell'Acqua Monica [email protected]
Delsante Simona [email protected]
Dessì Alessio [email protected]
Di Martino Simona [email protected]
Esposito Roberto [email protected]
Ferraro Francesco [email protected]
Fiorini Valentina [email protected]
Formenti Dario [email protected]
Gastaldo Federica [email protected]
Giorgi Simone [email protected]
Giovanninetti Stefano [email protected]
Gobetto Roberto [email protected]
Götzinger Alissa C. [email protected]
Houpis Ioannis [email protected]
Iazzetti Antonia [email protected]
Intrieri Daniela [email protected]
Lambruschini Chiara [email protected]
Less Giulio [email protected]
Licandro Emanuela [email protected]
Lucchesini Francesco [email protected]
Maccagno Massimo [email protected]
Maiorana Stefano [email protected]
Manca Gabriele [email protected]
Maner Asif [email protected]
85
Marcantoni Enrico [email protected]
Marchetti Fabio [email protected]
Martino Elisa [email protected]
Meazza Lorenzo [email protected]
Menendez Rodriguez Gabriel [email protected]
Mengozzi Luca [email protected]
Migliore Marco [email protected]
Milani Barbara [email protected]
Monari Magda [email protected]
Moni Lisa [email protected]
Monticelli Marco [email protected]
Mueller Thomas J.J. [email protected]
Nervi Carlo [email protected]
Papagni Antonio [email protected]
Penoni Andrea [email protected]
Peruzzini Maurizio [email protected]
Pettinari Riccardo [email protected]
Pettinari Claudio [email protected]
Piarulli Umberto [email protected]
Piermattei Pamela [email protected]
Ragaini Fabio [email protected]
Reginato Gianna [email protected]
Riccio Raffaele [email protected]
Riva Renata [email protected]
Robert Marc [email protected]
86
Ruffo Francesco [email protected]
Saccone Adriana [email protected]
Serrano Ruiz Manuel [email protected]
Sgarbossa Paolo [email protected]
Shamsi Javad [email protected]
Silva Ansaloni Lilian Marcia [email protected]
Sorana Federico [email protected]
Taptue Zubou Gaby Brice [email protected]
Tardia Piero [email protected]
Tubaro Cristina [email protected]
Vailati Facchini Sofia [email protected]
Vitali Forconesi Gabriella [email protected]
Zanotti Valerio [email protected]
Zuccaccia Cristiano [email protected]
87
List of Authors
Abbiati Giorgio OC5, OC17
Albani Clara P25
Albinati Alberto P18
Anselmo Manuel OC19
Ardizzoia G. Attilio OC20
Armirotti Andrea P25
Arnaboldi Serena OC6
Baldoli Clara P8
Bandini Marco P4
Banfi Luca OC10, P9, P22
Baron Marco OC9
Bartolini Matteo OC8
Basosi Riccardo OC8
Basso Andrea P22
Bea Michela OC20
Beley Marc OC21
Bellachioma Gianfranco OC22
Bellemin-Laponnaz Stéphane P1
Beller Matthias P16
Benincori Tiziana OC6
Bergamini Christian P4
Berkessel Albrecht P13
Bertani Roberta P18
88
Berti Erik P21
Bessi Matteo P23
Biffis Andrea OC9
Bisconti Lorenzo P7
Boitrel Bernard OC18
Bordoni Silvia P2
Borelli Tea P10
Borgia Vincenzo P4
Brenna Stefano OC20
Bresciani Giulio P17
Broggini Gianluigi P10
Bucci Alberto OC22
Buonanno Federico P7
Cacchi Sandro P12
Calamante Massimo OC8, P23
Calonghi Natalia P4
Calvanese Luisa OC15
Canepa Fabio OC10
Capacci Chiara OC11
Caporali Maria P5
Capriati Vito PL6,
Cardona Francesca KN1, P11
Carminati Daniela Maria OC18
Casarin Maurizio P18
Casella Girolamo P18
89
Caselli Alessandro OC17
Casiello Michele P19
Cauteruccio Silvia OC1, P8
Cerini Stefano P2
Cesarotti Edoardo P27
Cimino Alessandro OC23
Cingolani Andrea P14
Cinti Valentina OC sponsor, P29a, P29b, P29c
Cirilli Roberto OC6
Clerici Francesca OC5
Colombo Castelli Gabriele P27
Cometto Claudio OC4
Condello Francesca OC12
Conte Valeria OC16
Costa Mirco P6
Cozzi Pier Giorgio OC21
Cucciolito Maria Elena OC15
D’Adamio Giampiero P11
D’Auria Gabriella OC15
De Nisi Assunta P4
Della Ca Nicola P6
Dell’Acqua Monica OC5, OC17
Denißen Melanie P26
Dessì Alessio OC8
Di Donato Mariangela P23
90
Di Iulio Stefano P2
Di Nicola Corrado OC12
Dova Davide OC1, P8
EL-Atawy Mohamed A. P15
Esposito Roberto OC15
Fabrizi Giancarlo P12
Falcigno Lucia OC15
Fato Romana P4
Femoni Cristina OC11
Ferretti Francesco OC24, P3, P15, P16
Fiorini Valentina OC2, OC15
Floris Barbara OC16
Foggi Paolo P23
Formenti Dario OC24, P16
Franco Federico OC4
Gabriele Bartolo P6, P20
Galli Simona OC23
Gallo Emma PL4, OC18
Galloni Pierluca OC16
Gatto Emanuela OC16
Gelmi Maria Luisa OC5
Gennari Cesare P13
Gers-Panther Charlotte F. OC19
Giacoia Gabriele P6
Giorgi Simone P7
91
Giovanninetti Stefano P28
Gobetto Roberto OC3, OC4, P5
Goggiamani Antonella P12
Goti Andrea P11
Götzinger Alissa C. OC13, P24
Graiff Claudia OC9
Gros Philippe C. OC21
Gualandi Andrea OC21
Guanti Giuseppe P9
Habrant Damien P25
Heun Stefan P5
Hoppe Corinna OC13, P24
Houpis Ioannis KN4
Iagatti Alessandro P23
Iapalucci Maria Carmela OC11
Iazzetti Antonia P12
Ienco Andrea PL4, P5
Intrieri Daniela OC18
Junge Kathrin P16
Lambruschini Chiara OC10, P9
Le Gac Stéphane OC18
Licandro Emanuela OC1, P8
Lucarelli Carlo OC23
Lupi Flavia P11
Lupidi Gabriele P7
92
Macchioni Alceo OC22
Maffei Mathias P6
Manca Gabriele PL4, P5
Mancuso Raffaella P6, P20
Mandrup-Bertozzi Sine P25
Maner Asif P20
Mangione Giulia P18
Marcantoni Enrico PL3, P7
Marchetti Fabio KN2, OC7, OC12, P17
Marzo Tiziano P11
Maspero Angelo OC23
Massi Massimiliano OC2
Mazzoni Rita P14
Mealli Carlo PL4
Menendez Rodriguez Gabriel OC22
Mengozzi Luca OC21
Messori Luigi P11
Migliore Marco P25
Milani Barbara KN6
Mironova Valeriya OC3
Monari Magda P2, P4
Moni Lisa OC19, P22, P26
Monini Marco P23
Monticelli Marco OC9, P1
Morana Fabio OC10
93
Moreno-Sanz Guillermo P25
Mordini Alessandro OC8, P23
Mosca Nello OC12
Motti Elena P6
Mozzarelli Andrea OC5
Mozzon Mirto P18
Müller Thomas J.J. PL2, OC13, OC19, P24, P26
Mussini Patrizia R. OC6
Nencini Luca OC4
Nervi Carlo OC3, OC4
Oble Julie P10
Ortenzi Claudio P7
Palmisano Giovanni P21
Palmucci Jessica OC12
Pampaloni Guido P17
Pantolfi Gilberto P2
Papagni Antonio KN5
Pellegrino Sara OC5
Penoni Andrea OC6, P21
Peruzzini Maurizio PL1, PL4, OC8, P5
Petrini Agnese OC12
Pettinari Riccardo KN2, OC12,
Pettinari Claudio KN2, OC12
Pezzella Prisco OC15
Piano Riccardo OC5
94
Piarulli Umberto OC14, P13
Piccardo Marco P22
Piermattei Pamela P7
Pignataro Luca P13
Piomelli Daniele P25
Poli Giovanni P10
Ragaini Fabio OC24, P3, P15, P16
Reginato Gianna OC8, P23
Relini Annalisa OC10
Riani Paola OC10
Riva Renata OC10, OC19, P22, P26
Rizzato Silvia P18
Robert Marc PL5,
Ronda Luca OC5
Rossi Elisabetta OC5
Roviello Giuseppina OC15
Ruffo Francesco OC15,
Sabuzi Federica OC16
Sartor Giorgio P4
Sasso Oscar P25
Scarpelli Rita P25
Serrano Ruiz Manuel P5
Sgarbossa Paolo P18
Silva Ansaloni Lilian Marcia P3
Silvetti Fulvio OC10
95
Sinicropi Adalgisa OC8, P23
Spallarossa Martina P22
Squassabia Federico P28
Stagni Stefano OC2, OC15
Summa Maria P25
Sun Cunfa OC3
Surkus Annette-Enrica P16
Taddei Maurizio OC8
Talarico Giovanni OC15
Tamburini Sergio P18
Tarozzo Glauco P25
Tarroni Riccardo P2
Telesio Francesca P5
Tiravia Martina OC16
Toma Lucio OC18
Topf Christoph P16
Tseberlidis Giorgio OC17
Tubaro Cristina OC9, P1
Vailati Facchini Sofia P13
Valcarenghi Daniele OC17
Valentini Gianluca P26
Vecchi Andrea OC16
Velàsquez-Ochoa Juliana OC23
Venanzi Mariano OC16
Venzo Alfonso P18
96
Villa Silvia OC10
Vuerich Noemi OC21
Zacchini Stefano OC7, OC11, P17
Zani Lorenzo OC8, P23
Zanotti Valerio OC7, P14
Ziccarelli Ida P20
Zuccaccia Cristiano KN3, OC22