Optically Pure C1-Symmetric Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Asymmetric Olefin Metathesis

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

doi:10.1021/jacs.0c10705

Optically Pure C1-Symmetric Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Asymmetric Olefin Metathesis

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

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Abstract

An expedient access to the first optically pure ruthenium complexes containing C1-symmetric cyclic (alkyl)(amino)carbene ligands is reported. They demonstrate excellent catalytic performances in asymmetric olefin metathesis with high enantioselectivities (up to 92% ee). Preliminary mechanistic insights provided by density functional theory models highlight the origin of the enantioselectivity.

Original language	English (US)
Journal	Journal of the American Chemical Society
DOIs	https://doi.org/10.1021/jacs.0c10705
State	Published - Nov 13 2020

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10.1021/jacs.0c10705

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@article{63d841ef4cac4a7590eae992139ba16a,

title = "Optically Pure C1-Symmetric Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Asymmetric Olefin Metathesis",

abstract = "An expedient access to the first optically pure ruthenium complexes containing C1-symmetric cyclic (alkyl)(amino)carbene ligands is reported. They demonstrate excellent catalytic performances in asymmetric olefin metathesis with high enantioselectivities (up to 92% ee). Preliminary mechanistic insights provided by density functional theory models highlight the origin of the enantioselectivity.",

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

note = "KAUST Repository Item: Exported on 2020-11-16 Acknowledgements: We are grateful to the CNRS, the Ecole Nationale Superieure{\' }de Chimie de Rennes, the Aix-Marseille Universite, and the{\' } University of California San Diego. This work was supported by the Region Bretagne (ARED 2018 “Biometa” N° 601, grant to J.M.), the Agence Nationale de la Recherche (ANR-19- CE07-0017 ChiCAAC, R.J. and M.M.), and the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program, under Award DESC0009376 (G.B.). 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. For computer time, this research used the resources of the KAUST Supercomputing Laboratory (KSL) at KAUST.",

year = "2020",

month = nov,

day = "13",

doi = "10.1021/jacs.0c10705",

language = "English (US)",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Optically Pure C1-Symmetric Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Asymmetric Olefin Metathesis

AU - Morvan, Jennifer

AU - Vermersch, François

AU - Zhang, Ziyun

AU - Falivene, Laura

AU - Vives, Thomas

AU - Dorcet, Vincent

AU - Roisnel, Thierry

AU - Crévisy, Christophe

AU - Cavallo, Luigi

AU - Vanthuyne, Nicolas

AU - Bertrand, Guy

AU - Jazzar, Rodolphe

AU - Mauduit, Marc

N1 - KAUST Repository Item: Exported on 2020-11-16 Acknowledgements: We are grateful to the CNRS, the Ecole Nationale Superieure ́de Chimie de Rennes, the Aix-Marseille Universite, and the ́ University of California San Diego. This work was supported by the Region Bretagne (ARED 2018 “Biometa” N° 601, grant to J.M.), the Agence Nationale de la Recherche (ANR-19- CE07-0017 ChiCAAC, R.J. and M.M.), and the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program, under Award DESC0009376 (G.B.). 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. For computer time, this research used the resources of the KAUST Supercomputing Laboratory (KSL) at KAUST.

PY - 2020/11/13

Y1 - 2020/11/13

N2 - An expedient access to the first optically pure ruthenium complexes containing C1-symmetric cyclic (alkyl)(amino)carbene ligands is reported. They demonstrate excellent catalytic performances in asymmetric olefin metathesis with high enantioselectivities (up to 92% ee). Preliminary mechanistic insights provided by density functional theory models highlight the origin of the enantioselectivity.

AB - An expedient access to the first optically pure ruthenium complexes containing C1-symmetric cyclic (alkyl)(amino)carbene ligands is reported. They demonstrate excellent catalytic performances in asymmetric olefin metathesis with high enantioselectivities (up to 92% ee). Preliminary mechanistic insights provided by density functional theory models highlight the origin of the enantioselectivity.

UR - http://hdl.handle.net/10754/665952

UR - https://pubs.acs.org/doi/10.1021/jacs.0c10705

U2 - 10.1021/jacs.0c10705

DO - 10.1021/jacs.0c10705

M3 - Article

C2 - 33185429

SN - 0002-7863

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

ER -

Optically Pure C1-Symmetric Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Asymmetric Olefin Metathesis

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CCDC 1942929: Experimental Crystal Structure Determination : dichloro-{1-[2,6-bis(propan-2-yl)phenyl]-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene}-({5-nitro-2-[(propan-2-yl)oxy]phenyl}methylidene)-ruthenium unknown solvate

CCDC 2033132: Experimental Crystal Structure Determination : (+)(R)-dichloro-{1-[2,6-bis(propan-2-yl)phenyl]-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene}-({2-[(propan-2-yl)oxy]phenyl}methylidene)-ruthenium

CCDC 2033131: Experimental Crystal Structure Determination : dichloro-{1-[2,6-bis(propan-2-yl)phenyl]-3,5,5-trimethyl-3-(naphthalen-2-yl)pyrrolidin-2-ylidene}-({5-nitro-2-[(propan-2-yl)oxy]phenyl}methylidene)-ruthenium

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Optically Pure C1-Symmetric Cyclic(alkyl)(amino)carbene Ruthenium Complexes for Asymmetric Olefin Metathesis

Abstract

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CCDC 1942929: Experimental Crystal Structure Determination : dichloro-{1-[2,6-bis(propan-2-yl)phenyl]-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene}-({5-nitro-2-[(propan-2-yl)oxy]phenyl}methylidene)-ruthenium unknown solvate

CCDC 2033132: Experimental Crystal Structure Determination : (+)(R)-dichloro-{1-[2,6-bis(propan-2-yl)phenyl]-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene}-({2-[(propan-2-yl)oxy]phenyl}methylidene)-ruthenium

CCDC 2033131: Experimental Crystal Structure Determination : dichloro-{1-[2,6-bis(propan-2-yl)phenyl]-3,5,5-trimethyl-3-(naphthalen-2-yl)pyrrolidin-2-ylidene}-({5-nitro-2-[(propan-2-yl)oxy]phenyl}methylidene)-ruthenium

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