Merging Central and Axial Chirality in Cyclic(alkyl)(amino)carbenes: The Keystone for High Enantioselectivities in Ru-Catalyzed Asymmetric Olefin Metathesis

A series of 38 chiral ruthenium complexes containing cyclic-(alkyl)-(amino)-carbene (CAAC) ligands with axial C-N chirality have been developed. By merging axial and central chirality, very high enantioselectivity (up to >99% ee) as well as good to high <i>E</i>-selectivity (up to 98%) were achieved in the asymmetric ring-opening cross-metathesis (AROCM) of various norbornene and cyclopropene derivatives. Furthermore, these catalysts are efficient in challenging asymmetric ring-closing ene-yne metathesis (ARCEYM), providing valuable enantioenriched building blocks (up to 90% ee). Mechanistic insights from density functional theory (DFT) calculations highlight the crucial role of axial chirality in CAAC ligands in governing both enantio- and diastereo-selectivity in the metathesis reaction.

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Publication Details

Journal
JACS Au
Published
2025-10-13
DOI
https://doi.org/10.1021/jacsau.5c01098
Citations
2
Primary Topic
Synthetic Organic Chemistry Methods
Type
article
Field-Weighted Citation Impact
1.87
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article

Merging Central and Axial Chirality in Cyclic(alkyl)(amino)carbenes: The Keystone for High Enantioselectivities in Ru-Catalyzed Asymmetric Olefin Metathesis

Ziyun Zhang, Jakub Talcik, Laura Falivene, Thierry Roisnel et al.
2 citations
JACS Au
Synthetic Organic Chemistry Methods
1.87
article

Merging Central and Axial Chirality in Cyclic(alkyl)(amino)carbenes: The Keystone for High Enantioselectivities in Ru-Catalyzed Asymmetric Olefin Metathesis

Ziyun Zhang, Jakub Talcik, Laura Falivene, Thierry Roisnel, Luigi Cavallo, Muriel Albalat, Marc Mauduit, Jan Lorkowski, Rodolphe Jazzar, Nicolas Vanthuyne, Dylan Bouëtard, Thomas Vivès, Meng Liu
article en
2 citations

Abstract

A series of 38 chiral ruthenium complexes containing cyclic-(alkyl)-(amino)-carbene (CAAC) ligands with axial C-N chirality have been developed. By merging axial and central chirality, very high enantioselectivity (up to >99% ee) as well as good to high <i>E</i>-selectivity (up to 98%) were achieved in the asymmetric ring-opening cross-metathesis (AROCM) of various norbornene and cyclopropene derivatives. Furthermore, these catalysts are efficient in challenging asymmetric ring-closing ene-yne metathesis (ARCEYM), providing valuable enantioenriched building blocks (up to 90% ee). Mechanistic insights from density functional theory (DFT) calculations highlight the crucial role of axial chirality in CAAC ligands in governing both enantio- and diastereo-selectivity in the metathesis reaction.

JACS AuVol. 5(10)
Centre National de la Recherche Scientifique (FR), University of Salerno (IT), Université Rennes 2 (FR), University of California San Diego (US), Institute of Catalysis and Petrochemistry (RU), École Nationale Supérieure de Chimie de Rennes (FR), Centrale Méditerranée (FR), Université de Rennes (FR), King Abdullah University of Science and Technology (SA)
Openalex Percentile: Top 13%
Synthetic Organic Chemistry Methods
1.87
DOIOpen Access PDFOpenAlex
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