Cp*Co(Iii)-Catalyzed Coupling Of Benzamides With Alpha,Beta-Unsaturated Carbonyl Compounds: Preparation Of Aliphatic Ketones And Azepinones

A Cp*Co-III-catalyzed C-H functionalization of benzamide substrates with alpha,beta-unsaturated ketones has been optimized, providing a facile route towards aliphatic ketone products. When employing alpha,beta-unsaturated aldehydes as coupling partners, under the optimized protocol, a cascade reaction forming azepinones has also been developed. Finally, DFT studies have demonstrated how stabilization of a metallo-enol intermediate when employing alpha,beta-unsaturated ketones is the driving force leading to the observed aliphatic ketone product rather than olefinic products reported using ,-unsaturated esters as coupling partners.