Electrochemical Nickel-Catalyzed Asymmetric Hydrogenation of C═C Bonds Facilitated by a Proton-Coupled Electron Transfer Mediator

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-07-24 DOI:10.1021/acscatal.5c04130

Mengdi Li, and , Jonas C. Peters*,

引用次数: 0

Abstract

Enantioselective hydrogenation of C═C bonds is foundational to asymmetric synthesis, yet its adaptation to electrochemical methods has been limited by challenges in achieving chemoselectivity versus the hydrogen evolution reaction (HER). Here, we present a modular electrochemical strategy that merges chiral nickel catalysis with a cobaltocene-derived proton-coupled electron transfer (PCET) mediator to enable the asymmetric hydrogenation of α,β-unsaturated carbonyl compounds. Under optimized conditions, a range of substrates featuring diverse amide functionalities and substitution patterns are hydrogenated in high yields (up to 95%) and enantioselectivities (up to 98% ee). The results described highlight the potential benefits of mediator-assisted, fixed-potential electrocatalysis in selective, stereocontrolled hydrogenation under mild conditions.

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质子耦合电子转移介质催化镍催化C = C键的不对称氢化反应

C = C键的对映选择性加氢是不对称合成的基础，但它对电化学方法的适应受到实现化学选择性与析氢反应（HER）的挑战的限制。在这里，我们提出了一种模块化的电化学策略，将手性镍催化与钴二烯衍生的质子耦合电子转移（PCET）介质相结合，以实现α，β-不饱和羰基化合物的不对称氢化。在优化的条件下，一系列具有不同酰胺功能和取代模式的底物以高收率（高达95%）和对映选择性（高达98% ee）氢化。结果表明，在温和条件下，介质辅助的固定电位电催化在选择性立体控制氢化中的潜在优势。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.