A Short Synthesis of Natural (-)-Oblongolide via an Intramolecular or a Transannular Diels-Alder Reaction

Tony Kung Ming Shing, Jun Yang

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The absolute configuration of naturally occurring oblongolide is confirmed as (3aS,5aR,7S,9aS, 9bS)-3a,5a,6,7,8,9,9a,9b-octahydro-7,9b-dimethylnaphtho[1,2-c]furan-1(3H)-one (1) on the basis of a six-stage or an eight-stage synthesis from (-)-citronellol involving a steric-controlled, regioselective reduction and an intramolecular Diels-Alder (IMDA) reaction or a transannular Diels-Alder (TDA) reaction as the key steps. (—)-Citronellol (5) was converted into methyl (2E,4E,10.E)-(S)-(+)-11-(tert-butoxycarbonyl)-7-methylundeca-2,4,10-trienoate (7) by sequential Lemiuex-Johnson oxidation, Wittig olefination, pyridinium dichromate oxidation, and Wadsworth—Emmons—Homer alkenation. A regioselective reduction of the methoxycarbonyl group in 7 afforded ferč-butyl (2E,8E, 10E)-(S)-(+)-2,6-dimethyl-12-hydroxydodeca-2,8,10-trienoate (8) from which oblongolide (1) was obtained via an IMDA reaction. The macrocyclic (2E,8E,10E)-(S)-(+)-2,6-dimethyldodeca-2,8,10-trieno-1,12-lactone derived from 8 underwent a highly stereoselective TDA reaction to give 1 at a lower reaction temperature, in a shorter reaction time and in a better yield than the analogous IMDA reaction.

Original languageEnglish
Pages (from-to)5785-5789
Number of pages5
JournalJournal of Organic Chemistry
Volume60
Issue number18
DOIs
Publication statusPublished - 1995 Sep 1
Externally publishedYes

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Oxidation
Lactones
Temperature
citronellol
pyridinium dichromate
furan

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

A Short Synthesis of Natural (-)-Oblongolide via an Intramolecular or a Transannular Diels-Alder Reaction. / Shing, Tony Kung Ming; Yang, Jun.

In: Journal of Organic Chemistry, Vol. 60, No. 18, 01.09.1995, p. 5785-5789.

Research output: Contribution to journalArticle

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