Olefination via Cu-Mediated Dehydroacylation of Unstrained Ketones

The dehydroacylation of ketones to olefins is realized under mild conditions, which exhibits a unique reaction pathway involving aromatization-driven C-C cleavage to remove the acyl moiety, followed by Cu-mediated oxidative elimination to form an alkene between the alpha and beta carbons. The newly adopted N'- methylpicolinohydrazonamide (MPHA) reagent is key to enable efficient cleavage of ketone C-C bonds at room temperature. Diverse alkyl- and aryl-substituted olefins, dienes, and special alkenes are generated with broad functional group tolerance. Strategic applications of this method are also demonstrated.

Automated summary

The dehydroacylation of ketones to olefins can be achieved under mild conditions through a unique reaction pathway involving aromatization-driven C-C cleavage and Cu-mediated oxidative elimination. The newly adopted MPHA reagent plays a key role in enabling efficient cleavage of ketone C-C bonds at room temperature. This method allows for the generation of diverse alkyl- and aryl-substituted olefins with broad functional group tolerance, showcasing strategic applications.