Dioxirane Oxidation of 3-Arylideneflavanones: Diastereoselective Formation of trans,trans Spiroepoxides from the E Isomers

Csaba Nemes, Albert Lévai, Tamás Patonay, Gábor Tóth, Sándor Boros, Judit Halász, Waldemar Adam, Dieter Golsch

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34 Citations (Scopus)

Abstract

Oxidation of the E isomers of the 3-arylideneflavanones 1 by dimethyldioxirane in acetone solution at ambient temperature led to spiroepoxides trans,trans-2 in high yields (≥70%) and complete diastereoselectivity. Steric interaction with the axial aryl group in the 3-arylideneflavanone E-1 directs the attack of the dioxirane to the opposite side during the oxygen transfer to afford exclusively the trans,trans-2 epoxides, which clearly demonstrates the advantage of dimethyldioxirane as oxidant. In comparison, these substrates give under Weitz-Scheffer conditions (alkaline hydrogen peroxide) both diastereomeric epoxides (dr ca. 3:1) in poor yields (≤30%), while m-CPBA produces trans,- trans-2 spiroepoxides preferentially, but also in low yields (≤40%).1,2 Attempted epoxidation of the Z isomers afforded instead the 3-benzoylflavones 3 and/or 3-benzoylflavanones 4 in low yields. With the much more reactive methyl(trifluoromethyl)dioxirane, the E-1 isomers also gave the trans,- trans-2 spiroepoxides diastereoselectively in high yields, but the Z isomers suffered complete decomposition. Presumably the sterically hindered Z isomers encumber the oxygen atom transfer by the dioxirane and radical-type oxidation dominates for these reluctant substrates.

Original languageEnglish
Pages (from-to)900-905
Number of pages6
JournalJournal of Organic Chemistry
Volume59
Issue number4
DOIs
Publication statusPublished - Feb 1 1994

ASJC Scopus subject areas

  • Organic Chemistry

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