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"Cation-Stitching Cascade": exquisite control of terpene cyclization in cyclooctatin biosynthesis.

ABSTRACT: Terpene cyclization is orchestrated by terpene cyclases, which are involved in the biosynthesis of various cyclic natural products, but understanding the origin and mechanism of the selectivity of terpene cyclization is challenging. In this work, we describe an in-depth mechanistic study on cyclooctatin biosynthesis by means of theoretical calculations combined with experimental methods. We show that the main framework of cyclooctatin is formed through domino-type carbocation transportation along the terpene chain, which we call a "cation-stitching cascade", including multiple hydrogen-shifts and a ring rearrangement that elegantly determine the stereoselectivity.

SUBMITTER: Sato H

PROVIDER: S-EPMC4683443 | biostudies-literature | 2015 Dec

REPOSITORIES: biostudies-literature

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"Cation-Stitching Cascade": exquisite control of terpene cyclization in cyclooctatin biosynthesis.

Sato Hajime H Teramoto Kazuya K Masumoto Yui Y Tezuka Noriyuki N Sakai Kenta K Ueda Shota S Totsuka Yusuke Y Shinada Tetsuro T Nishiyama Makoto M Wang Chao C Kuzuyama Tomohisa T Uchiyama Masanobu M

Scientific reports 20151218

Terpene cyclization is orchestrated by terpene cyclases, which are involved in the biosynthesis of various cyclic natural products, but understanding the origin and mechanism of the selectivity of terpene cyclization is challenging. In this work, we describe an in-depth mechanistic study on cyclooctatin biosynthesis by means of theoretical calculations combined with experimental methods. We show that the main framework of cyclooctatin is formed through domino-type carbocation transportation alon ...[more]

PMID: 26681256

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