144.Photoredox‐Catalyzed Isomerization of Highly‐Substituted Allylic Alcohols via C‐H bond activation

Kai Guo, Zhongchao Zhang, Anding Li, Yuanhe Li, Jun Huang,* Zhen Yang,*

Angew. Chem. Int. Ed.2020, 59(28), 11660-11668

•C−H Activation | Hot Paper 

Photoredox‐catalyzed isomerization of γ‐carbonyl‐substituted allylic alcohols to their corresponding carbonyl compounds was achieved for the first time via C‐H bond activation . This catalytic redox‐neutral process provided a way for the synthesis of 1,4‐dicarbonyl compounds. Notably, allylic alcohols bearing tetrasubstituted olefins can also be transferred into their corresponding carbonyl compounds. The density functional theory calculations show that the carbonyl group at the γ‐position of allylic alcohols are beneficial to the formation of their corresponding allylic alcohol radicals with high vertical electron affinity, which contributes to the completion of the photoredox catalytic cycle.