Construction of three stereocenters via hydrogenative desymmetrization of 2,2,5-trisubstituted cyclohexane-1,3-diones

A Ru-catalyzed hydrogenative desymmetrization of 2,2,5-trisubstituted cyclohexane-1,3-diones was developed for construction of three stereocenters including two coherent and discontiguous chiral centers and a chiral quaternary carbon with excellent enantio- and diastereoselectivities. Stereodivergent synthesis of four stereoisomers could be conducted with high enantios-electivities. The desymmetrization could be achieved at gram scale without loss of reactivity and optical purity, and a formal synthesis of bioactive molecule (-)-isocelorbicol was completed.