Enantioselective Cyanofunctionalization of Aromatic Alkenes via Radical Anions

作者：Bin Zhang, Tiantian Li, Zhi-Cheng Mao, Min Jiang, Zhihan Zhang, Ke Zhao, Wen-Yuan Qu, Wen‐Jing Xiao, Jia‐Rong Chen · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.3c10439 · 被引用次数：98 · 研究领域：Radical Photochemical Reactions、Catalytic C–H Functionalization Methods、Sulfur-Based Synthesis Techniques

Alkene radical ions constitute an integral and unique class of reactive intermediates for the synthesis of valuable compounds because they have both unpaired spins and charge. However, relatively few synthetic applications of alkene radical anions have emerged due to a dearth of generally applicable and mild radical anion generation approaches. Precise control over the chemo- and stereoselectivity in alkene radical anion-mediated processes represents another long-standing challenge due to their high reactivity. To overcome these issues, here, we develop a new redox-neutral strategy that seamlessly merges photoredox and copper catalysis to enable the controlled generation of alkene radical anions and their orthogonal enantioselective cyanofunctionalization via distonic-like species. This new strategy enables highly regio-, chemo-, and enantioselective hydrocyanation, deuterocyanation, and cyanocarboxylation of alkenes without stoichiometric reductants or oxidants under visible light irradiation. This protocol provides a new blueprint for the exploration of the transformation potential of alkene radical anions.