Abstract Unsymmetrical PhCH CH(CH2X)(CO2Me) (X = Cl, OAc) undergoes regioselective α-substitution with AlMe3 to afford (E)-PhCH CH(Et)(CO2Me) under Ni(acac)2 catalysis. On the addition of planar chiral Ferrophite ligands [(R)-CpFe(1,2-C5H3Ar{P(OR)2}) (Ar = Ph, 4-CF3Ph, 3,5-Me2Ph, 1-naphthyl; (OR)2 = 1,1′-binaphthylene, 1,1′-biphenylene)] regioselective methylation γ to the leaving group is possible. It is proposed that the bulky Ferrophite ligand leads to an intermediate nickel allyl species NiII(Me)(Ferrophite){η3-PhCHCHCH(CO2Me)} that adopts a configuration whereby the PhCH terminus of the π-allyl and the Ni–Me are syn leading to good regio (up to 6.4:1) and stereo (up to 94% ee) selectivities.