Issue 30, 2025

A priori Design of [Mn(i)-Cinchona] catalyst for Asymmetric Hydrogenation of Ketones and β-Keto carbonyl Derivatives

Abstract

Herein, we report an efficient [Mncinchona] chiral catalytic system for the asymmetric hydrogenation of ketones, demonstrating a broad substrate scope and high chemoselectivity. The catalyst selectively reduces ketones, while leaving other reducible functional groups, such as olefins, alkynes, nitriles, nitro groups, and esters, unaffected. The solid-state structure of [Mncinchona] complex revealed that the cinchona ligand acts as bi-dentate ligand, providing valuable insights into its coordination environment and reaction mechanism. DFT calculations suggest that hydrogen molecule activation assisted by water molecules occurs via a six-membered transition state, with enantioselectivity driven by preferential hydride transfer to the si face of the prochiral substrate, resulting in the R configuration. This robust catalytic system shows potential for expansion to the reduction of β-ketoesters and γ-ketoamines and is expected to contribute to further advancements in asymmetric hydrogenation.

Graphical abstract: A priori Design of [Mn(i)-Cinchona] catalyst for Asymmetric Hydrogenation of Ketones and β-Keto carbonyl Derivatives

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Article information

Article type
Edge Article
Submitted
08 Apr 2025
Accepted
12 Jun 2025
First published
13 Jun 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2025,16, 13826-13837

A priori Design of [Mn(I)-Cinchona] catalyst for Asymmetric Hydrogenation of Ketones and β-Keto carbonyl Derivatives

S. Paira, N. Jain, D. Adhikari, R. B. Sunoj and B. Sundararaju, Chem. Sci., 2025, 16, 13826 DOI: 10.1039/D5SC02606G

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