Palladium-Catalyzed Domino Aminocarbonylation of Alkynols: Direct and Selective Synthesis of Itaconimides

[Image: see text] The first direct and selective synthesis of substituted itaconimdes by palladium-catalyzed aminocarbonylation of alkynols is reported. Key to the success of this transformation is the use of a novel catalyst system involving ligand L11 and appropriate reaction conditions. In the protocol here presented, easily available propargylic alcohols react with N-nucleophiles including aryl- and alkylamines as well as aryl hydrazines to provide a broad variety of interesting heterocycles with high catalyst activity and excellent selectivity. The synthetic utility of the protocol is demonstrated in the synthesis of natural product 11 with aminocarbonylation as the key step. Mechanistic studies and control experiments reveal the crucial role of the hydroxyl group in the substrate for the control of selectivity.