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Séminaire Chimie ED459

C–C and C–X bonds formation (X = O, S, F) from palladium/ligand chemistry : exploiting efficiently chloroarenes and C–H activation

Prof. Jean-Cyrille Hierso (équipe OMBC3 OrganoMétallique et Catalyse pour une Chimie Bio- et éco-Compatible, ICMUB Institut de Chimie Moléculaire de l’Université de Bourgogne, UMR 6302 CNRS, Dijon)

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Le Jeudi 28 mai 2015 à 13h45
UM FdS, salle dse cours SC-16.01

Polyphosphine ligands based on ferrocene platform have driven progress in applied,[1] and fundamental approaches of homogeneous catalysis.[2] The catalyst longevity and ultra-low catalyst loadings can be profitable to reach high turnover numbers in C–C couplings (TONs > 10,000).[3] These performances which are based on original multiphosphine cooperative effects are now used to develop efficient methods for Pd-catalyzed C–O and C–S cross-couplings. Direct C–H and O(or S)–H functionalization of demanding substrates including organic chlorides are feasible. Pd-catalyzed direct arylation,[4] alkylation,[5] etherification,[6] and thioetherification[7] reactions of heteroaromatics will be detailed. Mechanisms in oxidative addition and reductive elimination to Pd (electroanalysis, kinetics, DFT modeling) have revealed net differences with traditional monophosphine ligands that will be described.[8–10] We also particularly studied fundamental physical properties of constrained polyphosphines which are related to the intriguing phenomenon of nonbonded spin-spin nuclear J couplings.[12,13] Finally, C–H activation from palladium N-directing ligand chemistry has been successfully used for direct C–F fluorination of demanding N-heterocyclic substrates.[14]

References

1. (a) Hierso, J.-C. ; Fihri, A. ; Amardeil, R. ; Meunier, P. ; Doucet, H. ; Santelli, M. ; Ivanov V. V. Org. Lett. 2004, 6, 3473 ; (b) Ivanov, V. V. ; Hierso, J.-C. ; Amardeil, R. ; Meunier, P. Organometallics 2006, 25, 989.
2. (a) Hierso, J.-C. ; Fihri, A. ; Ivanov, V. V. ; Hanquet, B. ; Pirio, N. ; Donnadieu, B. ; Rebière, B. ; Amardeil, R. ; Meunier, P. J. Am. Chem. Soc. 2004, 126, 11077 ; (b) Mom, S. ; Beaupérin, M. ; Roy, D. ; Royer, S. ; Amardeil, R. ; Cattey, H. ; Doucet, H. ; Hierso, J.-C. Inorg. Chem. 2011, 50, 11592.
3. Doucet, H. ; Hierso, J.-C. Angew. Chem. Int. Ed. Engl. 2007, 46, 834.
4. (a) Roy, D. ; Mom, S. ; Beaupérin, M. ; Doucet, H. ; Hierso, J.-C. Angew. Chem. Int. Ed. 2010, 49, 6650 ; (b) Roy, D. ; Mom, S. ; Lucas, D. ; Cattey, H. ; Hierso, J.-C. ; Doucet, H. Chem. Eur. J. 2011, 17, 6453 ; (c) Roy, D. ; Mom, S. ; Royer, S. ; Lucas, D. ; H. ; Doucet, H. ; Hierso, J.-C. ACS Catalysis 2012, 2, 1033.
5. Wu, X. ; See, J. W. T. ; Xu, K. ; Hirao, H. ; Roger, J. ; Hierso, J.-C. ; Zhou, S. J. Angew. Chem. Int. Ed. Engl. 2014, 53, 13573.
6. Platon, M. ; Cui, L. ; Mom, S. ; Richard, P. ; Saeys, M. ; Hierso, J.-C. Adv. Synth. Catal. 2011, 353, 3403.
7. Platon, M. ; Wijaya, N. ; Rampazzi, V. ; Cui, L. ; Rousselin, Y. ; Saeys, M. ; Hierso, J.-C. Chem.−Eur. J. 2014, 20, 12584–12594.
8. Evrard, D. ; Lucas, D. ; Mugnier, Y. ; Meunier, P. ; Hierso, J.-C. Organometallics 2008, 27, 2643.
9. Zinovyeva, V. A. ; Luo, C.-H. ; Fournier, S. ; Devillers, C. H. ; Cattey, H. ; Doucet, H. ; Hierso, J.-C. ; Lucas, D. Chem.−Eur. J. 2011, 17, 9901.
10. Zinovyeva, V. A. ; Mom, S. ; Fournier, S. ; Devillers, C. H. ; Cattey, H. ; Doucet, H. ; Hierso, J.-C. ; Lucas, D. Inorg. Chem., 2013, 52, 11923.
12. Beaupérin, M. ; Smaliy, R. ; Cattey, H. ; Meunier, P. ; Ou, J. ; Toy, P. H. ; Hierso, J.-C. Chem. Commun. 2014, 50, 9505.
13. Hierso, J.-C. Chem. Rev. 2014, 114, 4838−4867.
15. Fleurat-Lessard, P. ; Roger, J. ; Testa, C. ; Hierso, J.-C. Theoretical study of (hetero)aromatic fluorination catalyzed by Pd. Abstracts of Papers, 249th ACS National Meeting, Denver, CO, United States, March 22-26, 2015, COMP-246.

Biographical Sketch. Jean-Cyrille Hierso was born in Toulouse in 1971. He studied physical chemistry at the Université P. Sabatier, where he worked on Pd nanochemistry (MS 1994, Dr. B. Chaudret, LCC-CNRS) and on CVD for heterogeneous catalysis (PhD 1997, Prof. P. Kalck). After postdoctoral research on scorpionate organometallic complexes (Prof. M. Etienne, LCC) and paints chemistry (Prof. J. Reedijk, Netherlands), in 2002 he was appointed Assistant Professor in Dijon. In 2006 he was awarded his Habilitation on the synthesis of ferrocenyl polyphosphanes and their application in homogeneous catalysis. He is full professor of Chemistry since 2009, heading the department of ‘‘Organometallic Chemistry and Catalysis’ (OMBC3) of the Institute of Molecular Chemistry at the University of Burgundy since 2011 (30 researchers, Dijon). His research interests include the properties and coordination chemistry of polydentate ligands applied in palladium catalysed cross-coupling reactions for C–C and C–X bond formation as well as the chemical vapor deposition of organics and organometallics for nanomaterials design. He has co-authored over 90 papers, reviews, patents and book chapters. In 2011, he was awarded the Prize for Coordination Chemistry from the French Chemical Society (SCF) and in 2012 he was distinguished by the EurJIC Young researcher Award and has been nominated junior Member of the Institut Universitaire de France (IUF).

Contact local ICGM : Dr. Yannick Guari, D.R. CNRS (équipe CMOS)

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