Palladium-catalyzed Z-alkenylative cross-coupling via β-alkenyl elimination of Z-allylic alcohols†

The transition metal-catalyzed Z-alkenylative cross-coupling has been well developed, but limitations remain in this methodology. Herein, we report a Z-alkenylative cross-coupling between Z-allylic alcohols and aryl bromides. The Z-alkenyl palladium species was generated in situ from β-alkenyl elimination of a Z-allylic alcohol, and it underwent coupling with electrophilic aryl bromides to furnish Z-alkenes with high yield and stereoselectivity. This process features mild reaction conditions, wide substrate scope and excellent functional group tolerance. Moreover, it has been successfully applied to the late-stage functionalization of natural products and drug molecules. Symmetric and unsymmetric Z-alkenylation products were obtained in synthetically valuable yields in this catalytic system.