Reaction of lithio anion derived from diethyl alkanephosphonate in the presence of 2 eq. of n-BuLi with benzenesulfonyl chloride gives directly the corresponding diethyl-1-chloro-1-lithioalkanephosphonate, which reacts in situ with carbonyl compounds followed by intramolecular substitution reaction to give 1,2-epoxyalkanephosphonates.