Palladium‐Catalyzed Crosscoupling Stereoselective Construction of Dienes via Z ‐Alkenylation of Vinyl Bromides

Transition‐metal‐catalyzed stereoselective synthesis of 1,3‐dienes has witnessed considerable progress in recent years, but significant limitations remain. In this study, we report a palladium‐catalyzed crosscoupling between Z ‐tertiary allylic alcohols and vinyl bromides via β ‐carbon elimination. This reaction proceeds under mild conditions and exhibits broad substrate scopes and excellent Z / E stereoselectivity, offering a valuable methodology for the construction of multisubstituted ( Z , E )‐dienes. Notably, this transformation enables efficient late‐stage Z ‐alkenylation of steroid derivatives. Moreover, the resulting diene undergoes a Diels–Alder reaction with maleic anhydride to afford the 1,4‐ cis‐endo monocyclic product.