A stereospecific synthesis of oxazolinyloxiranes

Lithiooxiranes 3a and 3b, generated by deprotonation of oxiranes 2a and 2b with s-BuLi at - 100 degreesC in Et2O, were found to be chemically very stable. trans-Lithiooxirane 3a was also configurationally stable and reacted stereospecifically with electrophiles to give 4a-k. In contrast, cis-lithiooxirane 3b was found to be configurationally much less stable and reacted with electrophiles affording mixtures of diastereomers 4, 7, and 8, After only a very short reaction time, 3b too reacted with electrophiles highly stereospecifically. Deprotonation-deuteration and deprotonation-alkylation of chiral oxazolinyloxiranes 12a and 12b to give oxiranes 12c and 12d were also examined. Semiempirical and ab initio calculations were carried out in an effort to explain the observed stereochemistry.