Photocatalysis Meets Copper Catalysis: A New Opportunity for Asymmetric Multicomponent Radical Cross-Coupling Reactions

作者：Peng‐Zi Wang, Bin Zhang, Wen‐Jing Xiao, Jia‐Rong Chen · 发表于：Accounts of Chemical Research · 年份：2024 · DOI：10.1021/acs.accounts.4c00638 · 被引用次数：105 · 研究领域：Catalytic C–H Functionalization Methods、Radical Photochemical Reactions、Sulfur-Based Synthesis Techniques

Conspectus In recent years, radical-mediated cross-coupling reactions have emerged as a compelling strategy for achieving a rich diversity in molecular topologies under benign conditions. However, the inherent high reactivity of radicals presents considerable challenges in controlling reaction pathways and selectivity, which often results in a limited range of substrates and a constrained reaction profile. Given the capacity of visible-light photoredox catalysis to generate a wide variety of reactive radicals and radical ions in a controlled manner and the propensity of copper complexes toward radical species, we envisaged that the synergy between chiral copper catalysts and photoactive catalysts would pave the way for developing innovative strategies. This integration is poised to unlock a broad spectrum of enantioselective multicomponent radical cross-coupling reactions. In this Account, we describe our insights and recent efforts in the realm of enantioselective multicomponent radical cross-coupling reactions. These advancements have been achieved through the innovative application of dual photoredox/copper catalysis or bifunctional copper catalysis under visible light irradiation. Our work is systematically divided into two sections based on the activation modes. The first section focuses on photoinduced copper-catalyzed chiral C–C and C–O bond formation through a radical addition/nucleophilic trap sequence. Our discussion of chiral C–C bond formation is particularly conc...