Remote Spin‐Center Shift Enables Activation of Distal Benzylic C─O and C─N Bonds

作者：Li-Wen Hui, Yee Lin Phang, Chenyang Ye, Jin‐Yu Lai, Feng‐Lian Zhang, Yao Fu, Yifeng Wang · 发表于：Angewandte Chemie · 年份：2025 · DOI：10.1002/ange.202506771 · 被引用次数：1 · 研究领域：Cyclopropane Reaction Mechanisms、Catalytic Cross-Coupling Reactions、Synthetic Organic Chemistry Methods

Abstract A spin‐center shift (SCS) is a radical process that commonly involves a 1,2‐radical shift along with the elimination of an adjacent leaving group by a two‐electron ionic movement. The conventional SCS process is largely limited to 1,2‐radical translocation, while a remote SCS event involving 1, n ‐radical translocation over a greater distance to enable distal bond functionalization remains largely underexplored. Herein, we report the boryl radical‐promoted distal deoxygenation and deamination of free benzylic alcohols and simple benzylic amines, respectively, through a remote SCS event. The reaction was initiated by the addition of a 4‐dimethylaminopyridine (DMAP)‐boryl radical to the carbonyl oxygen atom of a benzoate or benzamide. Then, radical translocation took place across the aromatic ring to promote benzylic C─O or C─N bond cleavage. The resulting radical intermediate subsequently coupled with various alkenes to afford a wide range of alkylated products. The proposed mechanistic pathway was supported by experimental investigations.