Fanny MORVAN PhD defense
Design of enantiomerically pure Cyclic (Alkyl)(Amino)Carbene ligands for rhodium and iridium-catalyzed asymmetric hydrogenation of functionalized alkenes and arenes
Vendredi 28 novembre, 14h00Passé
Organometallics: Materials & Catalysis (OMC) team
Abstract
Since the discovery of Cyclic (Alkyl)(Amino)Carbenes by Bertrand’s group in 2005, this new class of ancillary ligands has rapidly established itself in organometallic catalysis. The replacement of a nitrogen atom by a quaternary carbon center confers on these ligands unique electronic and steric properties, distinct from those of conventional diamino carbenes. Since 2019, various synthetic routes to access enantioenriched CAACs have been developed. Coordinated to transition metals, these ligands have led to remarkable enantioselectivities in ruthenium-catalyzed asymmetric olefin metathesis reactions (up to >99% ee) as well as in copper-catalyzed asymmetric conjugate borylation (up to 96% ee). In this context, this PhD work explores the application scope of chiral CAACs in rhodium and iridium-catalyzed asymmetric hydrogenation. Promising results have been obtained with enantiopure iridium-CAAC complexes in the hydrogenation of (E)-2,3 disubstituted allylic alcohols and derivatives, reaching up to 94% ee. Given the remarkable performance of rhodium-CAAC complexes in the chemoselective hydrogenation of functionalized (hetero)arenes involving heterogeneous active species, the development of this reaction in continuous-flow conditions was also investigated, including, for the first time, its evaluation in an asymmetric version.
Jury
Pr. Christophe DARCEL, Professor, ISCR, Rennes University / President
Dr. Alejandro PEREZ-LUNA, CNRS Research Director, IPCM, Sorbonne University / Reporter
Dr. Arnaud VOITURIEZ, CNRS Research Director, ICSN, Paris-Saclay University / Reporter
Dr. Laurence GRIMAUD, CNRS Research Director, ENS, Paris Sciences et Lettres / Examiner
Dr. Marc MAUDUIT, CNRS Research Director, ENSCR, ISCR, Rennes University / PhD Co-Director
Pr. Joanna WENCEL-DELORD, Professor, Julius-Maximilian University, Wurtzbourg, Germany / PhD Co-Director
Invited
Dr. Nicolas Vanthuyne, Aix-Marseille University
Contacts
Fanny Morvan, fanny.morvan@ensc-rennes.fr
Marc Mauduit, marc.mauduit@ensc-rennes.fr
