Tingting Miao, Rong‐Bin Liang, Xi Wang, Yonghong Xiao, Qing‐Xiao Tong, Jian‐Ji Zhong
The defluorinative coupling of fluoroalkenes with carbonyl compounds provides a direct and efficient strategy to valuable allylic alcohols. However, existing methods typically rely on transition-metal catalyst, stoichiometric reductants, or strongly reducing conditions. Herein, we report a photoredox catalyzed defluorinative coupling between fluoroalkenes and aliphatic carbonyls mediated by ligated boryl radicals, enabling the synthesis of both fluorinated and nonfluorinated allylic alcohols dictated by the choice of fluoroalkene substrate. This transition-metal-free protocol operates under mild conditions, exhibiting high Z / E stereoselectivity and broad substrate scope.