The experiments described here clarify the mechanism and origin of the enantioselectivity of the oxidation of racemic secondary alcohols catalyzed by chiral Mn(III)-salen complexes using HOBr, Br-2/H2O/KOAc or PhI(OAc)(2)/H2O/KBr as a stoichiometric oxidant. Key points of the proposed pathway include (1) the formation of a Mn(V) salen dibromide, (2) its subsequent reaction with the alcohol to give an alkoxy-Mn(V) species, and (3) carbonyl-forming elimination to produce the ketone via a highly organized transition state with intramolecular transfer of hydrogen from carbon to an oxygen of the salen ligand.