ch functionalization catalyzed by main group metals · ch functionalization catalyzed by main group...
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CHfunctionalizationcatalyzedbymaingroupmetals
PhD directors: Dr. Christophe Bour and Pr. Vincent Gandon E-mail: [email protected] and [email protected] Institution: Institut de Chimie Moléculaire et des Matériaux d’Orsay (ICMMO) Université Paris Sud Equipe Catalyse Moléculaire Bat 420 - 91405, Orsay, France BEFORE 31 MARCH Project: The efficient formation of carbon-carbon bonds is a milestone in organic synthesis. One of the most elegant methods is the use of catalytic C-H activation reactions for the functionalization and assembly of organic molecules of pharmaceutical interest and used in materials. In this context, the selective construction of C(sp2)-C(sp3) bonds between two molecular fragments has attracted more and more attention. While CH allylation is widely reported in the literature with numerous catalysts (Pd, Rh, Ru, Ir, Co, Cu, Mn, Fe…), 1 CH propargylation is poorly described,2, 3 especially when it involves the C-H functionalization of non-activated bonds. Alkynes or allenes with a leaving group may be good coupling partners. On the other hand, the selectivity of the reaction, the use of highly enriched aromatic nucleophiles or the need to use leaving groups still constitute strong limitations of the methods recently described. Also, we wish to increase this field of applications and to be able to use any nucleophiles, as well as sub-strate without directing groups. Preliminary results have shown that the concomitant use of a base and metal salts of group 13 can effectively promote this CH propargylation with various nucleophiles and substrates. This clearly shows that p-block metals offer many opportunities in catalysis that have not been studied so far in homogeneous catalysis.
Our team has been involved for several year in the discovery of new reactivities of group 13 complexes and their applications4 and we believe that we can open up, through this project, new horizons and make im-portant findings in Group 13 chemistry that would be of broad interest for the synthetic chemists communi-ty. PhD student will have opportunities to study molecular synthesis, organometallic chemistry and cataly-sis, to meet a large community of chemists and to participate in internal and external meetings and symposi-ums. This will give them solid and practical experiences to pursue their careers either in academic or indus-trial communities.
1 N. K. Mishra, S. Sharma, J. Park, S. Han, I. S. Kim, ACS Catal. 2017, 7, 2821. 2 C C. Zhu, J. L. Schwarz, S. Cembellín, S. Greßies, F. Glorius, Angew. Chem. Int. Ed. 2018, 57, 437. 3 (a) Y. Nishibayashi, Y. Inada, M. Yoshikawa, M. Hidai, S. Uemura, Angew. Chem. Int. Ed. 2003, 42, 1495 ; (b) J. J. Kennedy-Smith, L. A. Young, F. D. Toste, Org. Lett. 2004, 6, 1325 ; (c) R. Sanz, A. Martínez, J. M. Álvarez-Gutiérrez, F. Rodríguez, Eur. J. Org. Chem. 2006, 1383 ; (d) Y. -B. Yu, Z. -Ji, X. Zhang, Org. Lett. 2016, 18, 3302. 4 (a) M. Vayer, R. Guillot, C. Bour, V. Gandon, V.J. Org. Chem. 2018, 83, 11309; (b) M. Vayer, R. Guillot, C. Bour, V. Gandon, Chem. Eur. J. 2017, 23, 13901; (c) B. Michelet, S. Tang, G. Thiery, J. Monot, H. Li, R.Guillot, C. Bour, V. Gandon, Org. Chem. Front. 2016, 3, 1603.