The base solvolysis of some S-phosphorylated derivatives of 2-mercaptoethanol

Abstract

The preparation and base solvolyses of some S-phosphorylated derivatives of 2-mercaptoethanol and related compounds are reported. The fully esterified derivatives possessing favourable stereochemistry rearrange to the O-phosphorylated derivatives which then undergo elimination of an episulphide. In contrast, the mono-esterified derivatives eliminate alkoxide to give the cyclic intermediate [graphic omitted](:O)·O^–. This undergoes nucleophilic attack with preferential P–O cleavage and thus contrasts with the behaviour of acyclic analogues. These reactions are discussed in terms of pentacovalent intermediates.