The synthesis of drug-like saturated cycloalkanes is more complex than their two-dimensional aromatic analogues. A formidable challenge lies in synthesizing all isomers of multi-substituted cycloalkanes. Now a cobalt-catalysed system enables diastereodivergent hydroalkylation of substituted methylenecyclohexanes with exceptional versatility. Strategic manipulation of ligands provides access to all isomers of disubstituted cyclohexanes, piperidines and multi-substituted cyclohexanes.