Synthesis, characterization, polymerization of optically active terminal epoxides and episulfides bearing bulky groups

Abstract

A simple and efficient protocol was developed for the syntheses of optically active epoxides(2a–2d) via the reactions of epichlorohydrin with organometallic reagents with steric hindrance at low temperature. On this basis, episulfides(3a–3d) were obtained with high e.e. values by the reaction of the corresponding epoxides with NH₄SCN. The configuration of thiiranes was opposite to that of the corresponding epoxides. Then, epoxides 2a–2d were anionically polymerized and the poly-R-2a(or poly-S-2a) was proved to keep a stable one-handed helical conformation in solution. The oligomers[degree of polymerization(DP)=2–5] were obtained when the thiiranes(3a, 3b and 3c) were used to polymerize.

Keywords

Optical activity / Epoxide / Episulfide / One-handed helicity

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