Direct Acylation of Alkyl and Aryl Bromides via Nickel-Catalyzed Aldehyde C–H Functionalization

Aldehyde C–H activation followed by coupling of the acyl fragment with a nucleophile or electrophile represents a straightforward method for accessing ketones. Although this strategy has been utilized for the formation of ketones with diverse substitution patterns, most methods are tailored for ketones that possess aromatic functionality derived from either or both substrates involved in the catalytic union. Herein, we describe the development of acylation reactions of alkyl and aryl bromides to directly access ketones from aliphatic and (hetero)aromatic aldehydes. Judicious choice of tridentate (terpyridine) or bidentate (phenanthroline) ligands enables sp3 and sp2 bromides to participate as coupling partners. Potential for diacylation and orthogonality via iterative couplings are also demonstrated.