Diastereoselective Synthesis of Tetrahydrofurans via Reaction of γ,δ-Epoxycarbanions with Aldehydes^†

Hydroxymethyl-substituted tetrahydrofurans were prepared with high diastereoselectivity by reaction of the carbanion derived from 3,4-epoxybutyl phenyl sulfone with aldehydes in the presence of a mixture of lithium and potassium tert-butoxides. Initial formation of aldol-type adducts is a nondiastereoselective but reversible process; thus, subsequent formation of one main diastereoisomer is controlled by the relative rates of cyclization. The configuration of the carbon stereocenter at the oxirane ring is inverted in the course of the S_N2 process, and two new centers are created diastereoselectively.