Abstract
A (XantPhos)Pd-catalyzed decarbonylative C-H functionalization of azoles with difluoromethyl anhydrides is reported. Under the optimized conditions, azole substrates react selectively at the C(2)-position to afford CF(2)H-substituted benzoxazole, oxazole, benzothiazole, thiazole, and benzimidazole products. Organometallic mechanistic studies reveal that XantPhos enforces an unusual seesaw geometry of the key Pd(II)(CF(2)H)(carboxylate) intermediate, which may be responsible for the effectiveness of this ligand.