State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, P. R. China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Nat Commun. 2022 Jun 8;13(1):3302. doi: 10.1038/s41467-022-30655-3.
Different from the traditional two-electron oxidative addition-transmetalation-reductive elimination coupling strategy, visible light has been successfully integrated into transition metal-catalyzed coupling reaction of propargylic alcohol derivatives highly selectively forming allenenitriles: specifically speaking, visible light-mediated Cu-catalyzed cyanation of propargylic oxalates has been realized for the general, efficient, and exclusive syntheses of di-, tri, and tetra-substituted allenenitriles bearing various synthetically versatile functional groups. A set of mechanistic studies, including fluorescence quenching experiments, cyclic voltammetric measurements, radical trapping experiments, control experiments with different photocatalyst, and DFT calculation studies have proven that the current reaction proceeds via visible light-induced redox-neutral reductive quenching radical mechanism, which is a completely different approach as compared to the traditional transition metal-catalyzed two-electron oxidative addition processes.
与传统的双电子氧化加成-转金属化-还原消除偶联策略不同，可见光已成功整合到炔丙醇衍生物的过渡金属催化偶联反应中，高选择性地形成了 allenylnitriles：具体来说，可见光介导的 Cu 催化炔丙基丙二酸酯的氰化反应已实现了二取代、三取代和四取代的 allenylnitriles 的通用、高效和专一地合成，这些 allenylnitriles 带有各种合成多功能的官能团。一系列的机理研究，包括荧光猝灭实验、循环伏安测量、自由基捕获实验、不同光催化剂的对照实验和 DFT 计算研究，证明了当前反应是通过可见光诱导的氧化还原中性还原猝灭自由基机理进行的，与传统的过渡金属催化的双电子氧化加成过程完全不同。
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