Aerobic Coupling of Organophosphonium Salts with Alkenes: Catalyst‐Free C(sp3)−C(sp2) Bond Formation

Abstract An aerobic coupling of benzhydryl phosphonium salts with simple alkenes for accessing trisubstituted olefins is developed under metal‐free, catalyst‐free, and additive‐free conditions. New C( sp 3 )−C( sp 2 ) bond is constructed via the C−P and C−H bond functionalization by synergistically using O 2 as a “green” oxidant and DMSO as a promoter. The method also distinguishes itself by its broad substrate scope and synthetic potential. Particularly, the use of 1,3,5‐trimethoxybenzene fragment in the resulting products as a carbon‐based leaving group for further transformations is proved to be feasible.