Construction of Distant Stereocenters by Enantioselective Desymmetrizing Carbonyl–Ene Reaction

An efficient desymmetrizing carbonyl–ene reaction of 1-substituted 4-methylenecyclohexanes with glyoxal derivatives was thus executed by a chiral N,N′-dioxide/Ni^II catalyst, providing facile access to cyclohexene derivatives bearing two remote 1,6-related stereocenters. This distal stereocontrol methodology originates from the efficient interaction between the catalyst with enophiles, discrimination of the two chair conformations of olefinic components, and the intrinsic six-membered transition-state structure of ene process.