Low-temperature n-butyllithium-induced rearrangement of allyl 1,1-dichlorovinyl ethers

ORGN 955

Thomas G. Minehan, thomas.minehan@csun.edu, Aaron Christopher, and Stephen Kelly. Department of Chemistry and Biochemistry, California State University, Northridge, 18111 Nordhoff Street, Northridge, CA 91330
Upon treatment with n-butyllithium at -78°C, a variety of allyl-1,1-dichlorovinyl ethers undergo rapid sigmatropic rearrangement to furnish γ,δ-unsaturated esters, thioesters, or amides after alcohol, thiol or amine addition. Compounds containing quaternary centers 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 β-C-glycosides and α,β-disubstituted lactones. Evidence delineating a possible mechanistic pathway for this reaction will be presented.