A method for the preparation of an allylic sulfide comprises contacting an activated sulfenyl compound of Formula (I) with a thiol of Formula (II) for a period of time sufficient to form an intermediate of Formula (III), and contacting the intermediate of Formula (III) with a thiophilic agent, in a polar solvent, to induce a [2,3]-sigmatropic rearrangement therein and thereby form an allylic sulfide of Formula (IV), with concomitant loss of a sulfur atom to the thiophilic agent, wherein in Formulas (I, II, II, and IV), X is S or SO.sub.2; Y is an aryl group, a substituted-aryl group, a heteroaryl group , or a substituted heteroaryl group; R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are each independently H, a hydrocarbon moiety or a substituted hydrocarbon moiety; and R is an organic moiety.