Mechanistic Insight into Weak Base‐Catalyzed Generation of Carbon Monoxide from Phenyl Formate and Its Application to Catalytic Carbonylation at Room Temperature without Use of External Carbon Monoxide Gas

Abstract. The mechanisms of weak-base-catalyzed generation of carbon monoxide (CO) and phenol from phenyl formate were investigated by experimental and theoretical methods. Kinetic studies revealed a first-order reactionin both phenyl formate and the base. The reaction was found to proceed by an E2 α-elimination pathway, which involves the abstraction of the formyl proton of phenyl formate, simultaneously generating CO and phenoxide. The reaction rate was affected by the substituents of phenyl formate, the polarity of solvents, and the basicity of bases. The mechanistic insight obtained from these studies permitted the chemical control of the rate of CO generation, which were key to the development of the external-CO-free Pd-catalyzed phenoxycarbonylation of haloarenes at room temperature. Because of the mild reaction conditions and wide substrate scope, this phenoxycarbonylation constitutes a general, safe, and practical method to synthesize arenecarboxylic acid esters.