Chiral 2-alkynoate derivatives of 4-substituted oxazolidin-2-ones and of Oppolzer's 10,2-camphorsultam have been synthesized in good to excellent yields using a one-pot method involving the nucleophilic attack of the lithium salt or the lithium chloride complex of the chiral auxiliary on a mixed 2-alkynoic-pivalic anhydride. (C) 1997 Elsevier Science Ltd.