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

doi:10.1021/ol052916m

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

Org Lett. 2006 Mar 16;8(6):1041-4. doi: 10.1021/ol052916m.

Authors

Isamu Shiina¹, Tadafumi Uchimaru, Mitsuru Shoji, Hideaki Kakeya, Hiroyuki Osada, Yujiro Hayashi

Affiliation

¹ Department of Applied Chemistry, Faculty of Science, and Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan. shiina@ch.kagu.tus.ac.jp

PMID: 16524263
DOI: 10.1021/ol052916m

Abstract

[reaction: see text] 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.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Crystallography, X-Ray
Cyclization
Epoxy Compounds / chemical synthesis*
Epoxy Compounds / chemistry
Hydrogen Bonding
Hydroquinones / chemical synthesis*
Hydroquinones / chemistry
Molecular Structure

Substances

Epoxy Compounds
Hydroquinones
epoxytwinol A