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

doi:10.1021/acs.organomet.3c00054

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 journal › Article › peer-review

10 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 language	English (US)
Journal	Organometallics
DOIs	https://doi.org/10.1021/acs.organomet.3c00054
State	Published - 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

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10.1021/acs.organomet.3c00054

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

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.",

author = "Jennifer Morvan and Fran{\c c}ois Vermersch and Ziyun Zhang and Thomas Vives and Thierry Roisnel and Christophe Cr{\'e}visy and Laura Falivene and Luigi Cavallo and Nicolas Vanthuyne and Guy Bertrand and Rodolphe Jazzar and Marc Mauduit",

note = "KAUST Repository Item: Exported on 2023-03-10 Acknowledgements: The authors are grateful to the CNRS, the Ecole Nationale Sup{\'e}rieure de Chimie de Rennes, the Aix-Marseille Universit{\'e}, 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 Gu{\'e}gan, Elsa Caytan, and the PRISM core facility (Biogenouest, UMS, Biosit, Universit{\'e} de Rennes 1) for NMR experiments. They are grateful to Philippe J{\'e}han and the CRMPO core facility for HMRS.",

year = "2023",

month = mar,

day = "7",

doi = "10.1021/acs.organomet.3c00054",

language = "English (US)",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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T1 - Ambivalent Role of Rotamers in Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Enantioselective Ring-Opening Cross-Metathesis

AU - Morvan, Jennifer

AU - Vermersch, François

AU - Zhang, Ziyun

AU - Vives, Thomas

AU - Roisnel, Thierry

AU - Crévisy, Christophe

AU - Falivene, Laura

AU - Cavallo, Luigi

AU - Vanthuyne, Nicolas

AU - Bertrand, Guy

AU - Jazzar, Rodolphe

AU - Mauduit, Marc

N1 - 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.

PY - 2023/3/7

Y1 - 2023/3/7

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/690221

UR - https://pubs.acs.org/doi/10.1021/acs.organomet.3c00054

U2 - 10.1021/acs.organomet.3c00054

DO - 10.1021/acs.organomet.3c00054

M3 - Article

SN - 0276-7333

JO - Organometallics

JF - Organometallics

ER -

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

Abstract

Bibliographical note

ASJC Scopus subject areas

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