The Sakurai reaction of N-alkoxycarbonylamino sulfones (α-amido sulfones) with allyltrimethylsilane in the presence of gallium (III) chloride (5 mol%) proceeded smoothly to afford the corresponding protected homoallylamines in high yields (82–96%). As an application of this methodology, two-step synthesis of biologically active natural products, 2, 6-disubstituted piperidine alkaloid derivatives was carried out.