Ru(II)-Catalyzed Controlled Cross-Dehydrogenative Coupling of Benzamides with Activated Olefins via Weakly Coordinating Primary Amides.

Abstract

Ru(II)-catalyzed regioselective ortho-alkenylation of primary benzamides with activated olefins has been realized over the competitive cyclized products. This reaction overall proceeds via a cross-dehydrogenative coupling (CDC) reaction using a simple and weakly coordinating primary amide group in the presence of an inexpensive Ru(II) salt and allows the controlled introduction of olefin motifs at the ortho-position of benzamides. The key to the success of this strategy depends on fine-tuning the reaction conditions. The developed protocol has demonstrated excellent regio/diastereoselectivity and a good functional group tolerance with wide substrate scope and obviates the requirement of external auxiliaries as well as the costly metal catalyst. Detailed mechanistic studies indicate the involvement of the base-assisted internal electrophilic-type substitution (BIES) step in the reaction mechanism.