Switchable Selectivity in the Pd-Catalyzed Alkylative Cross-Coupling of Esters

The Pd-catalyzed cross-coupling of phenyl esters and alkyl boranes is disclosed. Two reaction modes are rendered accessible in a selective fashion by interchange of the catalyst. With a Pd–NHC system, alkyl ketones can be prepared in good yields via a Suzuki–Miyaura reaction proceeding by activation of the C­(acyl)–O bond. Use of a Pd–dcype catalyst enables alkylated arenes to be synthesized by a modified pathway with extrusion of CO. Applications of this divergent coupling strategy and the origin of the switchable selectivity are discussed.