Computational study on the reaction mechanism of the key thermal [4 + 4] cycloaddition reaction in the biosynthesis of epoxytwinol A.
[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.
Shiina
Isamu
I
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
Uchimaru
Tadafumi
T
Shoji
Mitsuru
M
Kakeya
Hideaki
H
Osada
Hiroyuki
H
Hayashi
Yujiro
Y
D018360:Crystallography, X-Ray; D003500:Cyclization; D004852:Epoxy Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006860:Hydrogen Bonding; D006873:Hydroquinones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure
D004852:Epoxy Compounds; D006873:Hydroquinones; C496191:epoxytwinol A