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Well-defined Rhodium and Iridium complexes containing chiral Cyclic(alkyl)(amino)carbenes for asymmetric hydrogenation

14 July 2025, Version 1
Working Paper
This content is an early or alternative research output and has not been peer-reviewed by Cambridge University Press at the time of posting.

Abstract

A novel class of well-defined rhodium and iridium complexes containing various chiral cyclic(alkyl)(amino)carbene (ChiCAAC) ligands has been synthesised and fully characterized. While no enantioselectivity was observed with chiral Rh-CAAC, the Ir-CAAC counterparts demonstrated good performances in the asymmetric hydrogenation of various allylic alcohols and derivatives with up to 86% ee. Mechanistic studies, including deuteration experiments revealed that the reduction proceeds via direct alkene hydrogenation rather than via isomerization.

Keywords

CAAC
asymmetric catalysis
Hydrogenation
Iridium
Rhodium

Supplementary materials

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Materials availability
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All data supporting the findings of this study are available within the article and the supplemental information or from the lead contact upon reasonable request.
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Version History

Jul 14, 2025 Version 1

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The content is available under CC BY NC ND 4.0 [opens in a new tab]

DOI

10.26434/chemrxiv-2025-ls2ps
D O I: 10.26434/chemrxiv-2025-ls2ps [opens in a new tab]

Funding

Région Bretagne
ARED n°2671
CNRS
Prematuration Program 2023 (H2*CAAC)
European Commission
ERC-SG AlCHIMIE no.949804

Author’s competing interest statement

The author(s) have declared they have no conflict of interest with regard to this content

Ethics

The author(s) have declared ethics committee/IRB approval is not relevant to this content

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