A synthetic alternative to the type-II intramolecular 4 + 3 cycloaddition reaction

Richard S Grainger; Richard B Owoare; Patrizia Tisselli; Jonathan W Steed

doi:10.1021/jo034356f

A synthetic alternative to the type-II intramolecular 4 + 3 cycloaddition reaction

J Org Chem. 2003 Oct 3;68(20):7899-902. doi: 10.1021/jo034356f.

Authors

Richard S Grainger¹, Richard B Owoare, Patrizia Tisselli, Jonathan W Steed

Affiliation

¹ Department of Chemistry, King's College London, Strand, London WC2R 2LS. richard.grainger@kcl.ac.uk

PMID: 14510576
DOI: 10.1021/jo034356f

Abstract

Oxyallyl cations generated in situ from dihaloketones have been found to undergo the Favorskii rearrangement in preference to an intramolecular Type-II 4 + 3 cycloaddition reaction in trifluoroethanol and hexafluoropropan-2-ol solvents, generating acrylate esters with high cis selectivity. A synthetic alternative to the intramolecular Type-II 4 + 3 cycloaddition has been developed on the basis of intramolecular enolate alkylation to close a 7-membered ring with an exocyclic double bond.