Synthesis of Enantioenriched 1,2‐cis Disubstituted Cycloalkanes by Convergent NiH Catalysis

Abstract Enantioenriched multi‐substituted cycloalkanes constitute an essential class of compounds in pharmaceuticals, natural products and agrochemicals. Here we report an NiH‐catalyzed asymmetric migratory hydroalkylation process for the efficient and selective construction of such compounds. Through a dynamic kinetic asymmetric transformation (DYKAT), easily accessible racemic and isomeric mixtures of cycloalkenes could be directly utilized as starting materials, convergently producing thermo‐dynamically disfavored chiral 1,2‐ cis disubstituted cycloalkanes bearing vicinal stereocenters with high levels of regio‐, diastereo‐ and enantioselectivity. In addition, prochiral cyclic alkenes can be also employed, and deliver chiral 1,2‐ cis disubstituted cycloalkanes through desymmetrization process.