The control of selectivity in the reactions of the highly reactive open‐shell carbon radicals is an attractive but often challenging task. Building on the strategy of photoinduced iminyl radical‐mediated C−C bond cleavage, we have developed photocatalytic neophyl rearrangement and reduction of distal carbon radicals under visible light irradiation of O‐acyl oximes. This mild protocol tolerates a wide range of readily available O‐acyl oximes, enabling facile synthesis of diversely substituted α,β‐unsaturated nitriles and β‐functionalized saturated nitriles in a highly selective manner.

中文翻译：

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由亚甲基自由基介导的CC键断裂引起的光催化新叶重排和远端碳自由基的还原

控制高反应性开壳碳自由基反应中的选择性是一项有吸引力的任务，但通常具有挑战性。在光诱导的亚胺基自由基介导的C-C键裂解策略的基础上，我们开发了在O-酰基肟的可见光照射下光催化的新菌重排和远端碳自由基的还原。这种温和的方案可耐受各种现成的O-酰基肟，从而能够以高度选择性的方式轻松合成各种取代的α，β-不饱和腈和β-官能化的饱和腈。