Deoxygenative Arylation of Allylic/Benzylic Esters through Cooperative Photoredox/Nickel Catalysis.

The versatile transformations of allylic intermediates can offer efficient synthetic pathways for complex natural products and pharmaceutical molecules. While conventional allylic substitution reactions like the Tsuji-Trost reaction typically operate through a two-electron transfer mechanism with nucleophilic partners, we herein report a photoredox/nickel dual-catalyzed deoxygenative arylation of allylic or benzylic esters with aryl iodides through a single-electron transfer process. This method achieves 100% linear selectivity in producing allylic arylation products while exhibiting exceptional functional group tolerance including ester, nitrile, halides, boron, and heterocycles. The applicability for the late-stage functionalization of various natural products also underscores the synthetic utilities of this method.