Abstract

AbstractAerobic 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.

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