A wide selection of phosphine activators has been screened to improve the selection process in the asymmetric Appel reaction. Of the activators screened, hexachloroacetone (HCA) gave the highest selectivity with excellent yield, but at least one of its by-products, pentachloroacetone (PCA), can become involved in the selection process. In addressing this, a new reaction of phosphines with oxalyl chloride was discovered that can also generate the key intermediate chlorophosphonium salt (CPS), gives better enantioselectivity and possesses significant advantages over other phosphine activators.