Aminocarbonylation of Aryl Halides to Produce Primary Amides by Using NH4HCO3 Dually as Ammonia Surrogate and Base

Article abstract of DOI:10.1002/cctc.201700893

An efficient and clean protocol was developed for rapid production of primary aromatic amides by aminocarbonylation with NH₄HCO₃. Without addition of auxiliary base, the use of solid and cheap NH₄HCO₃ dually as ammonia surrogate and base not only promoted aminocarbonylation over subsequent dehydration and hydrolysis of amides owing to its weak basicity, and it also made the reaction manipulation clean and simplified without the presence of stinky NH₃ or organic amines. The Xantphos ligand with relatively intensive π-acceptor character (¹J_31P–77Se=758 Hz) and wide natural bite angle (β_n=111°) was found to be indispensable for the high efficiency of this reaction.