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Chemistry Seminar

Friday 14 November 2014, 1.00PM to 2:00pm

Speaker(s): Professor Jean-Cyrille Hierso, University of Burgundy


The development of polydentate ligands based on ferrocene platform has driven progress in homogeneous catalysis.[1-3]Catalyst longevity and ultra-low catalyst loadings have been used to reach high turnover numbers (TONs > 10,000). These performances were based on original multidentarity effects, which are now used to develop very efficient methods for palladiumcatalysed C–C, C–N and C–O (C–S) cross-couplings, thus direct C–H and O(S)–H functionalizations of demanding substrates including organic chlorides are feasible. The features of robust, air-stable polyphosphine auxiliaries and their performances in recent low loading palladium-catalyzed reactions in direct arylation and etherification (or thioetherification) reactions of heteroaromatics will be detailed.[4,5,6] Mechanisms in oxidative addition and reductive elimination (electroanalysis, kinetics, DFT modeling) have revealed net differences with traditional monophosphine ligands that will be described.[6-12] Finally, the physical properties of constrained polyphosphines related to the intriguing phenomenon of nonbonded spin-spin nuclear J couplings will be discussed.[13]

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. Roy, D.; Mom, S.; Beaupérin, M.; Doucet, H.; Hierso, J.-C. Angew. Chem. Int. Ed. 2010, 49, 6650. 5. Roy, D.; Mom, S.; Lucas, D.; Cattey, H.; Hierso, J.-C.; Doucet, H. Chem.−Eur. J. 2011, 17, 6453. 6. Platon, M.; Cui, L.; Mom, S.; Richard, P.; Saeys, M.; Hierso, J.-C. Adv. Synth. Catal. 2011, 353, 3403. 7. Evrard, D.; Lucas, D.; Mugnier, Y.; Meunier, P.; Hierso, J.-C. Organometallics 2008, 27, 2643. 8. 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. 9. Roy, D.; Mom, S.; Royer, S.; Lucas, D.; H.; Doucet, H.; Hierso, J.-C. ACS Catalysis, 2012, 2, 1033. 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. 11. Beaupérin, M.; Smaliy, R.; Cattey, H.; Meunier, P.; Ou, J.; Toy, P. H.; Hierso, J.-C. Chem. Commun. 2014, 50, 9505. 12. Platon, M.; Wijaya, N.; Rampazzi, V.; Cui, L.; Rousselin, Y.; Saeys, M.; Hierso, J.-C. Chem.−Eur. J. 2014, 20, 12584-12594. 13. Hierso, J.-C. Chem. Rev. 2014, 114, 4838−4867.

Please contact Ian Fairlamb if you would like more details.

Location: C/A102