Neighboring Effect of Intramolecular Chlorine Atoms on Epoxide Opening Reaction by Chloride Anions.

We investigated the diastereoselectivity of ring openings for chloro vinyl epoxides with various chlorination reagents. In the chlorinolysis reactions using vinyl epoxides having an allyl alcohol, inversion:retention ratios varied depending on the chloride sources. In limited cases, the increase in retention ratio was consistent with the intervention of chloronium ions. In contrast, all vinyl epoxides bearing an α,β-unsaturated ester gave only the inversion products. These results suggest the electron-withdrawing property suppressed the chloronium ions.