Low-Temperature N -Butyllithium-Induced Rearrangement Of Allyl 1,1-Dichlorovinyl Ethers

Upon treatment with n-BuLi at low temperatures, a variety of allyl 1,1-dichlorovinyl ethers 2 undergo rearrangement to furnish γ,δ-unsaturated esters 3 after alcohol addition. Compounds containing quaternary centers (3e: R1 = H, R2, R3 = −(CH2)5−; 3f: R1 = H, R2 = CH3, R3 = (CH2)2CH(CH3)2) may be formed in high yield and under mild conditions utilizing this protocol. The reaction is stereospecific and may be applied to the preparation of Δ2,3-β-C-glycosides and α,β-disubstituted lactones.