Stereoselective Nickel-Catalyzed Iterative 1,2-Reduction of Trisubstituted Enones to Cycloalkanols Bearing Two Contiguous Stereocenters

Herein we first report a nickel-catalyzed asymmetric iterative 1,2-reduction of trisubstituted enones to cycloalkanols with two contiguous stereocenters in high yields with excellent diastereo- and enantioselectivities (36 examples, up to 98.5:1.5 er, >20:1 dr, TON = 500). The combined experimental and computational mechanistic studies suggested energy changes during two consecutive reduction processes and provided a range of unique mechanistic rationales that have not been disclosed in nickel-catalyzed asymmetric hydrogenation-related studies.