Computational Studies on Biosynthetic Carbocation Rearrangements Leading to Quiannulatene: Initial Conformation Regulates Biosynthetic Route, Stereochemistry, and Skeleton Type
- 11 October 2018
- journal article
- research article
- Published by Wiley in Angewandte Chemie-International Edition
- Vol. 57 (45), 14752-14757
- https://doi.org/10.1002/anie.201807139
Abstract
The results of quantum chemical calculations on the mechanism of the carbocation cascade of reactions in the biosynthetic pathways leading to the pentacyclic sesterterpenes quiannulatene and sesterfisherol provide reasonable answers to several persistent mechanistic questions in sesterterpene biosynthesis, including (1) the reaction pathways of the multi‐cyclic ring system construction and skeletal rearrangements, (2) the mechanism of triquinane skeleton formation, which requires more complicated rearrangements than previously proposed, (3) the stereochemistry of the final carbocation intermediate, and (4) the determining factor of biosynthetic selection of 5/6/4/6/5 or 5/6/5/5/5 pentacyclic skeleton formation. This in‐depth mechanistic study on sesterterpene biosynthesis revealed that the shape of the final product and the type of triquinane skeleton formed are regulated by the stereochemistry and conformation of the common starting material, geranylfarnesyl diphosphate (GFPP).Keywords
Funding Information
- Japan Society for the Promotion of Science (17H06173, 17H05430, JP16H06454, JP16H06443)
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