Conversion of Unsaturated Alcohols into Functionalized Tetrahydrofurans and Tetrahydropyrans via Nitrile Oxide Dipolar Cycloadditions

Alfred Hassner, K. S.K. Murthy, Albert Padwa, Ugo Chiacchio, Dennis C. Dean, Allen M. Schoffstall

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83 Scopus citations

Abstract

The intramolecular nitrile oxide cycloaddition (INOC) of a series of unsaturated oximino ethers has been investigated. The synthesis of the olefinic nitrile oxides involves treating an unsaturated alcohol with aα-bromoalkanal O-(trimethylsilyl) oxime in the presence of fluoride ion followed by subsequent sodium hypochlorite oxidation. The nitrile oxides were not isolated but spontaneously underwent intramolecular cycloaddition to give fused five- and six-membered ring ethers. The preferred stereoisomer in the formation of the five-membered ring ethers is trans, whereas in the six-membered ring ethers the cis isomer predominates. MM2 calculations help rationalize the observed stereoselectivity. The ratio of diastereomeric products from the INOC reaction appears to correlate with product stabilities. Simple heating of some of the oximino ethers led to intramolecular cycloaddition. The ring closure apparently proceeds subsequent to a tautomeric equilibration of the oxime with a transient nitrone which is trapped by the neighboring π-bond.

Original languageEnglish
Pages (from-to)5277-5286
Number of pages10
JournalJournal of Organic Chemistry
Volume54
Issue number22
DOIs
StatePublished - 1 Oct 1989

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