Carboxylic Acid-Enabled Vinylene Transfer Reaction by Co(III) Catalyst: Scope and Applications to the Five-Step Total Synthesis of Protoberberine Alkaloids Containing Free Hydroxyl Group without Protection.

A Co(III)-catalyzed vinylene transfer reaction enabled by carboxylic acid is presented. This redox-neutral transformation tolerates various functional groups, including free hydroxyl groups, and features practicality. Five-step routes based on the vinylene transfer reaction and Heck annulation have been devised to the total synthesis of 8-oxodehydrodiscretamine and 2-demethyl-oxypalmatine without the protection of the free hydroxyl functionality.