Asymmetric Catalytic Radical Reactions Enabled by Chiral N,N′-Dioxide–Metal Complexes

作者：Weidi Cao, Xiaohua Liu, Xiaoming Feng · 发表于：Accounts of Chemical Research · 年份：2025 · DOI：10.1021/acs.accounts.5c00370 · 被引用次数：37 · 研究领域：Radical Photochemical Reactions、Oxidative Organic Chemistry Reactions、Catalytic C–H Functionalization Methods

Conspectus The strategic implementation of asymmetric catalytic radical reactions has evolved into a sophisticated methodology for constructing stereogenic centers, driven by remarkable advancements in radical generation techniques. However, achieving high stereoselectivity remains a formidable challenge due to the inherent high reactivity, transient lifetime of radical species, and presence of competing racemic background pathways. Addressing these limitations necessitates precise catalytic systems capable of orchestrating radical generation and enantioselective transformation in a controlled manner. In this Account, we systematically present our recent progress in enantioselective radical transformations mediated by chiral N, N ′-dioxide–metal complexes, which have previously been widely used in polar reactions. Our mechanistic investigations categorize these transformations into three distinct paradigms based on radical generation strategies. (1) Oxidant-driven radical generation: Leveraging oxidants─hypervalent iodine reagents, peroxides, or molecular oxygen─we achieved alkyl radical formation. By synergizing these oxidants with redox-active or redox-inert chiral N,N ′-dioxide-metal catalysts, we accomplished asymmetric difunctionalization of both electron-deficient and electron-rich olefins, alongside enantioselective radical cross-coupling reactions. (2) Merging photocatalytic strategy: Visible light irradiation facilitates the activation of metallic or organic photocat...