Palladium‐Catalyzed Oxidative Cross‐Coupling of α‐Cyanoketene Dithioacetals with Olefins

Efficient palladium‐catalyzed cross‐coupling reactions of the internal olefins α‐cyanoketene dithioacetals with a variety of olefins were achieved in dioxane/HOAc/DMSO (9:3:1 v/v/v) under air atmosphere or by means of AgOAc as the terminal oxidant. Electron‐deficient terminal olefins reacted to form the linear diene derivatives with air as the oxidant. Styrenes underwent the cross‐coupling to give both the linear and branched dienes when using AgOAc as the oxidant. Unactivated cyclic and linear internal olefin substrates both reacted in the presence of a catalytic amount of benzoquinone in air to produce skipped dienes. The typical products were structurally confirmed by X‐ray crystallography.