Remote Spin‐Center Shift Enables Activation of Distal Benzylic C─O and C─N Bonds
Abstract
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.
Article Details
Authors (7)
Li‐Wen Hui
State Key Laboratory of Precision and Intelligent Chemistry Anhui Provincial Key Laboratory of Biomass Chemistry Department of Chemistry University of Science and Technology of China 96 Jinzhai Road Hefei Anhui 230026 China
Yee Lin Phang
State Key Laboratory of Precision and Intelligent Chemistry Anhui Provincial Key Laboratory of Biomass Chemistry Department of Chemistry University of Science and Technology of China 96 Jinzhai Road Hefei Anhui 230026 China
Chen‐Yang Ye
State Key Laboratory of Precision and Intelligent Chemistry Anhui Provincial Key Laboratory of Biomass Chemistry Department of Chemistry University of Science and Technology of China 96 Jinzhai Road Hefei Anhui 230026 China
Jin‐Yu Lai
Institute of Advanced Technology University of Science and Technology of China 96 Jinzhai Road Hefei Anhui 230026 China
Feng‐Lian Zhang
State Key Laboratory of Precision and Intelligent Chemistry Anhui Provincial Key Laboratory of Biomass Chemistry Department of Chemistry University of Science and Technology of China 96 Jinzhai Road Hefei Anhui 230026 China
Yao Fu
State Key Laboratory of Precision and Intelligent Chemistry, Anhui Province Key Laboratory of Biomass Chemistry
Yi‐Feng Wang
State Key Laboratory of Precision and Intelligent Chemistry Anhui Provincial Key Laboratory of Biomass Chemistry Department of Chemistry University of Science and Technology of China 96 Jinzhai Road Hefei Anhui 230026 China