Cobalt-Catalyzed Acceptorless Dehydrogenation of Alcohols to Carboxylate Salts and Hydrogen

Abstract

The facile oxidation of alcohols to carboxylate salts and H₂ is achieved using a simple and readily accessible cobalt pincer catalyst (NNN^HtBuCoBr₂). The reaction follows an acceptorless dehydrogenation pathway and displays good functional group tolerance. The amine-amide metal-ligand cooperation in cobalt catalyst is suggested to facilitate this transformation. The mechanistic studies indicate that in-situ-formed aldehydes react with a base through a Cannizzaro-type pathway, resulting in potassium hemiacetolate, which further undergoes catalytic dehydrogenation to provide the carboxylate salts and H₂.