Aerobic Self‐Esterification of Alcohols Assisted by Mesoporous Manganese and Cobalt Oxide

Abstract Aerobic self‐esterification of primary alcohols catalyzed by mesoporous metal oxides (manganese and cobalt oxides) is reported under base and solvent free conditions. For a range of aliphatic alcohols, up to 90 % conversions to esters was achieved. The catalytic reaction is likewise applicable to neat aldehydes as substrates with yields of up to 86 %. High pressure batch reaction for ethanol to ethyl acetate led to 22 % yield. Isotope labeling studies indicated decarboxylation on the catalyst surface. Mechanistic and kinetic experiments implicate oxygen rebound and α‐carbon removal as intermediate steps. Mesoporous cobalt oxide showed about 20 % higher catalytic activity compared to mesoporous manganese oxide.