Computational study on the reaction mechanism of the key thermal [4 + 4] cycloaddition reaction in the biosynthesis of epoxytwinol A

Isamu Shiina, Tadafumi Uchimaru, Mitsuru Shoji, Hideaki Kakeya, Hiroyuki Osada, Yujiro Hayashi

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The key [4 + 4] cycloaddition in the biosynthesis of epoxytwinol A has been established by theoretical calculations to comprise of three processes. The first step is formation of the C8-C8′ bond generating a biradical intermediate. Next, rotation about the C8-C8′ bond occurs, and finally the C1-C1′ bond is formed. Biradicals stabilized by conjugation and two hydrogen bonds are essential for realization of this rare thermal [4 + 4] cycloaddition.

Original languageEnglish
Pages (from-to)1041-1044
Number of pages4
JournalOrganic Letters
Volume8
Issue number6
DOIs
Publication statusPublished - 2006 Mar 16

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ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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