DFT study on selective autocatalyzed α-alkylation of ketones with alcohols

•DFT calculations were performed on selective autocatalyzed α-alkylation of ketones with alcohols.•Ketones are not only the reactants, but also are the initiators that facilitate the formation of the catalytic aldehydes.•Reaction temperature and alcohol concentration govern the production selectivity.•Dioxygen can further enhance the ketone product selectivity.