The reaction of 4-lithio-2,2-dimethyl-1,3-oxathiane 3,3-dioxide with various electrophiles is presented. Acylation of the anion provided labile 4-acyl-2,2-dimethyl-1,3-oxathiane 3,3-dioxides which underwent desulfonation with silica gel to produce gamma-hydroxy ketones with three carbon unit elongation. Thus, 4-lithio-2,2-dimethyl-1,3-oxathiane 3,3-dioxide was shown to be a useful synthetic equivalent of a gamma-hydroxypropyl anion. Methyl esters proved to be the best acylating agents in this reaction. Synthetic utility of this carbon chain elongation was illustrated by the syntheses of dl-lanceol and dl-dihydrojasmone.

Abstract2,2‐Dimethyl‐1,3‐oxathiane (I) is oxidized to the sulfone (II), which is lithiated to (III) and subsequently treated with electrophilic reagents, such as the alkylating agents (IV) and the carbonyl derivatives (VI), to yield the substituted sulfones (V) and (VII).