环氧twinol A生物合成中关键热[4+4]环加成反应机理的计算研究

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

作者信息

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

机构信息

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.

出版信息

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

DOI:10.1021/ol052916m

PMID:16524263

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.

摘要

[反应：见正文] 通过理论计算确定，环氧twinol A生物合成中的关键[4 + 4]环加成反应由三个过程组成。第一步是形成C8-C8'键，生成双自由基中间体。接下来，围绕C8-C8'键发生旋转，最后形成C1-C1'键。通过共轭和两个氢键稳定的双自由基对于实现这种罕见的热[4 + 4]环加成反应至关重要。