Enantiospecific Syntheses of (+)-Crotepoxide, (+)-Boesenoxide, (+)-β-Senepoxide, (+)-Pipoxide Acetate, (-)-iso-Crotepoxide, (-)-Senepoxide, and (-)-Tingtanoxide from (-)-Quinic Acid

Tony Kung Ming Shing, Eric K.W. Tam

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

A convenient strategy that is ideally suited for the construction of all the naturally occurring cyclohexane diepoxides and cyclohexene epoxides is described. The key intermediate 12, a 1,3-cyclohexadiene, has been prepared from (-)-quinic acid in 11 steps with 18% overall yield. Singlet oxygen photooxygenation of the 1,3-cyclohexadiene followed by rearrangement of the resultant endoperoxides with either cobalt-meso-tetraphenylporphyrin or trimethyl phosphite afforded enantiopure (+)-crotepoxide, (+)-boesenoxide, and (-)-iso-crotepoxide or (-)-senepoxide, (+)-β-senepoxide, (+)-pipoxide acetate, and (-)-tingtanoxide, respectively.

Original languageEnglish
Pages (from-to)1547-1554
Number of pages8
JournalJournal of Organic Chemistry
Volume63
Issue number5
Publication statusPublished - 1998 Mar 6
Externally publishedYes

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Quinic Acid
trimethyl phosphite
Acetates
Singlet Oxygen
Epoxy Compounds
Cobalt
futoxide
boesenoxide
1,3-cyclohexadiene

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

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abstract = "A convenient strategy that is ideally suited for the construction of all the naturally occurring cyclohexane diepoxides and cyclohexene epoxides is described. The key intermediate 12, a 1,3-cyclohexadiene, has been prepared from (-)-quinic acid in 11 steps with 18{\%} overall yield. Singlet oxygen photooxygenation of the 1,3-cyclohexadiene followed by rearrangement of the resultant endoperoxides with either cobalt-meso-tetraphenylporphyrin or trimethyl phosphite afforded enantiopure (+)-crotepoxide, (+)-boesenoxide, and (-)-iso-crotepoxide or (-)-senepoxide, (+)-β-senepoxide, (+)-pipoxide acetate, and (-)-tingtanoxide, respectively.",
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