2. Academic Validation
  3. "Cation-Stitching Cascade": exquisite control of terpene cyclization in cyclooctatin biosynthesis

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

  • Sci Rep. 2015 Dec 18:5:18471. doi: 10.1038/srep18471.
Hajime Sato 1 2,  Kazuya Teramoto 3,  Yui Masumoto 1 2,  Noriyuki Tezuka 1 2,  Kenta Sakai 4,  Shota Ueda 4,  Yusuke Totsuka 4,  Tetsuro Shinada 4,  Makoto Nishiyama 3,  Chao Wang 1 2,  Tomohisa Kuzuyama 3,  Masanobu Uchiyama 1 2
Affiliations

Affiliations

  • 1 Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
  • 2 Elements Chemistry Laboratory, RIKEN, and RIKEN Center for Sustainable Resource Science (Wako campus), 2-1 Hirosawa, Wako-shi, Saitama-ken 351-0198, Japan.
  • 3 Biotechnology Research Center, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan.
  • 4 Department of Material Science, Graduate School of Science, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan.
PMID: 26681256 DOI: 10.1038/srep18471
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.

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