Manganese-Catalyzed Hydrogen-Autotransfer C−C Bond Formation: α-Alkylation of Ketones with Primary Alcohols

A novel catalytic hydrogen-autotransfer protocol for the atom-efficient alpha-alkylation of ketones with readily available alcohols is presented. The use of manganese complexes bearing non-innocent PNP pincer ligands enabled the functionalization of a broad range of valuable ketones, including 2-oxindole, estrone 3-methyl ether, and testosterone. Mechanistic investigations suggest the participation of an intramolecular amidate-assisted alcohol-dehydrogenation process.