Ambivalent Role of Rotamers in Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Enantioselective Ring-Opening Cross-Metathesis

Jennifer Morvan, François Vermersch, Ziyun Zhang, Thomas Vives, Thierry Roisnel, Christophe Crévisy, Laura Falivene, Luigi Cavallo, Nicolas Vanthuyne, Guy Bertrand, Rodolphe Jazzar, Marc Mauduit

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

The development of highly efficient enantioselective olefin metathesis catalysts is a significant challenge. Using optically pure chiral cyclic (alkyl)(amino)carbene (ChiCAAC) ligands combined with preliminary mechanistic insights and density functional theory (DFT) computations, we show that catalytic performances in this field can be impaired by the formation of rotamers before the enantio-determining step. Using DFT, we also demonstrate that these results can help accelerate the process of ligand discovery by providing faster methods to discriminate potential candidates.
Original languageEnglish (US)
JournalOrganometallics
DOIs
StatePublished - Mar 7 2023

Bibliographical note

KAUST Repository Item: Exported on 2023-03-10
Acknowledgements: The authors are grateful to the CNRS, the Ecole Nationale Supérieure de Chimie de Rennes, the Aix-Marseille Université, and the University of California San Diego. This work was supported by the Region Bretagne (ARED 2018 “Biometa” No 601, grant to J.M.), the Agence Nationale de la Recherche (ANR-19-CE07-0017 ChiCAAC), and the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program, under Award # DE-SC0009376. L.C., L.F., and Z.Z. thank the King Abdullah University of Science and Technology (KAUST) for supporting this work. For computer time, this research used the resources of the KAUST Supercomputing Laboratory (KSL) at KAUST. Umicore AG & Co is acknowledged for a generous gift of ruthenium complexes. M.M. and T.V. thank Shimadzu and Chiral Technology for their support in the separation of chiral molecules by supercritical fluid chromatography (SFC) technology. The authors are grateful to Jean-Paul Guégan, Elsa Caytan, and the PRISM core facility (Biogenouest, UMS, Biosit, Université de Rennes 1) for NMR experiments. They are grateful to Philippe Jéhan and the CRMPO core facility for HMRS.

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint

Dive into the research topics of 'Ambivalent Role of Rotamers in Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Enantioselective Ring-Opening Cross-Metathesis'. Together they form a unique fingerprint.

Cite this