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

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

Research output: Contribution to journal › Article › peer-review

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 language	English
Pages (from-to)	1041-1044
Number of pages	4
Journal	Organic Letters
Volume	8
Issue number	6
DOIs	https://doi.org/10.1021/ol052916m
Publication status	Published - 2006 Mar 16
Externally published	Yes

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/ol052916m

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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.",

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AU - Shiina, Isamu

AU - Uchimaru, Tadafumi

AU - Shoji, Mitsuru

AU - Kakeya, Hideaki

AU - Osada, Hiroyuki

AU - Hayashi, Yujiro

PY - 2006/3/16

Y1 - 2006/3/16

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AB - 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.

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

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