Reaction of 2-Ethoxy-5-methyl-1,3,2-dioxaphosphorinane-5-methanol 2-Sulfide and 4-Methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-Sulfide With Sulfuryl Chloride: Mechanistic and Stereochemical Considerations

Abstract

Treatment of either cis- or trans-2-ethoxy-5-methyl-1,3,2,-dioxaphosphorinane-r-5-methanol 2-sulfide with SO₂Cl₂ yielded the cyclization product 4-methyl-2,6,7-trioxa-1-phosphabicyclo-[2.2.2]octane 1-oxide. In contrast, treatment of 4-methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]-octane 1-sulfide with the same reagent gave stereospecific ring opening to trans-2-chloro-5-methyl-1,3,2-dioxaphosphorinane-r-5-methyl chloride 2-oxide.