Enantioselective Remote Alkylation Enabled by Metallaphotoredox Catalysis via Selective C–C Bond Cleavage

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2025-01-23 DOI:10.1021/acscatal.4c07460

Yu Ao, Ning Wang, Si-Yuan Tang, Zhan-Jie Wang, Liang-Hua Zou, Huan-Ming Huang

引用次数: 0

Abstract

Despite recent advances in enantioselective radical coupling with strained cyclic rings, asymmetric radical reactions triggered by unstrained cyclic motifs remain rare. Herein, we report a mild and general strategy for activating a diverse set of readily available unstrained cyclic alcohols for the remote and site-specific allylic alkylation of ketones through a combination of photoredox-mediated proton-coupled electron transfer and chiral chromium catalysis. This newly developed dual catalytic system exhibits extensive applicability, operates under mild conditions, offers straightforward operation, and demonstrates tolerance to diverse functional groups. The open-shell strategy has also been applied in the late-stage modification of complex drug and natural product derivatives with high levels of enantioselectivity.

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通过选择性C-C键切割金属光氧化还原催化实现对映选择性远端烷基化

尽管近年来对映选择性自由基与应变环偶联的研究取得了进展，但由非应变环基序引发的不对称自由基反应仍然很少。在这里，我们报告了一种温和和通用的策略，通过光氧化还原介导的质子偶联电子转移和手性铬催化的组合，激活多种容易获得的无张力环醇，用于酮的远程和位点特异性烯丙基烷基化。这种新开发的双催化系统具有广泛的适用性，在温和的条件下运行，提供简单的操作，并表现出对不同官能团的耐受性。开壳策略也被应用于具有高水平对映体选择性的复杂药物和天然产物衍生物的后期修饰。

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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.