Palladium-Catalyzed Decarbonylative Borylation of Aryl Anhydrides.

A palladium-catalyzed base-free decarbonylative borylation of aryl anhydrides has been developed. Catalyst system consisting of Pd(OAc)2/dppb enables readily available aryl anhydrides to be employed as electrophiles for the synthesis of versatile arylboronate esters via O-C(O) bond activation and decarbonylation. This method is characterized by an excellent functional group tolerance and broad substrate scope, using bench stable aryl anhydrides as aryl electrophiles in C-B bond formation. Mechanistic studies and functionalization of late-stage pharmaceutical molecules are disclosed.