The regioselectivity of α-metalation–methylation of N-BF3 adducts of 4-(dimethylamino) pyridines as a function of β-substitution is examined in attempts to prepare configurationally stable atropisomeric derivatives (I and II) having an α-methyl substituent and a β-biaryl stereogenic axis. The activity of some of these derivatives as catalysts for acyl transfer is examined and the kinetic resolution of 1-(1-naphthyl) ethanol catalysed by α-methyl chiral ...