Abstract Enantioselective Ni-catalysed methylation of Baylis–Hillman-derived allylic electrophiles in the presence of ferrophite ligands has been investigated computationally and experimentally. The sense and degree of enantioselectivity attained is independent of both the leaving group and the isomeric structure of the initial allylic halide. DFT studies support the selective formation of a limited number of energetically favoured anti and syn ...