A novel synthetic approach to racemic a-substituted a-amino acids is described. The key intermediates of this methodology are highly electrophilic iminium ions, bearing carbonyl substituents at both the iminium carbon and nitrogen atom. The preparation of precursors 8, loa-, and 12 includes electrochemical oxidation techniques according to literature procedures. When an a-methyl precursor (8 or loa) was used, reactions with allylsilanes ...