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

• DOI: 10.1002/adsc.201700751
• Publication Date: 2017-08-26T04:36:41Z
• Authors: Hideyuki Konishi; Mika Matsubara; Keisuke Mori; Takaki Tokiwa; Sundaram Arulmozh...; Yuta Yamamoto; Yoshinobu Ishikawa; Hiroshi Hashimoto; Yasuteru Shigeta; Hiroaki Tokiwa; Kei Manabe
• Keywords: Carbonylation; Methyl formate; Base (topology)

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