Racemic and enantioenriched alkynyl-glycinols can be synthesized by Lewis acid catalyzed cyclization reaction of bis-trichloracetimidates derived from alkynyl-glycols. The cyclization proceeds selectively to give 4-alkynyl-oxazolines as the propargylic substitution products. Enantioenriched bis-imidates that contain an alkyl or trimethylsilyl substituent at the acetylene gave oxazolines with complete inversion of configuration. In turn, considerable racemization was observed in the cyclization of bis-imidates that contain a phenyl substituent. The racemization for these substrates can be suppressed by introduction of the electronegative substituent at the phenyl ring. Oxazolines prepared by bis-imidate cyclization reaction can be readily transformed to protected alkynyl-glycol derivatives. Racemic and enantioenriched alkynyl-glycinol derivatives can be synthesized by Lewis acid catalyzed cyclization reaction of bis-trichloroacetimidates into oxazolines.