The iridium complex {H2 [graphic omitted] H2Me][(P)–NMe2]}[(P)–NMe2= o- (diphenylphosphino)-N, N-dimethyl aniline] formed by intramolecular CH oxidative addition, as shown by X-ray analysis, behaves as a chemoselective catalyst in hydrogen transfer reduction of α, β-unsaturated ketones to unsaturated alcohols.