Semipinacol rearrangement of a bicyclo[7.2.0]undecane framework into a bicyclo[6.3.0]undecane skeleton: A model study on the biosynthesis of seiridiasteriscane A

Osamu Ishibashi, Mami Nishiyama, Eunsang Kwon, Masaru Hashimoto, Shigefumi Kuwahara, Masaru Enomoto

Research output: Contribution to journalArticlepeer-review

Abstract

Seiridiasteriscane A is an asteriscane-type sesquiterpenoid bearing a trans-fused bicyclo[6.3.0]undecane skeleton. Although its biosynthesis has been proposed to involve a semipinacol rearrangement of a putative intermediary acetate bearing a bicyclo[7.2.0]undecane ring system (presumably derived from coisolated pestalotiopsin M) followed by epimerization of the resulting cis-fused seiridiasteriscane B, such a type of semipinacol rearrangement has never been reported so far. Our model study revealed that a 1-hydroxybicyclo[7.2.0]undecan-2-yl acetate underwent a smooth and stereospecific semipinacol rearrangement with the assistance of Et2AlCl to give the corresponding bicyclo[6.3.0]undecane-9-one. In addition, the resulting cis-fused 5,8-bicyclic ketone was partially epimerized to the corresponding trans-fused ketone by prolonged adsorption onto a silica gel plate. These results may support a recently proposed biosynthetic pathway of seiridiasteriscane A.

Original languageEnglish
Pages (from-to)1621-1627
Number of pages7
JournalBioscience, Biotechnology and Biochemistry
Volume85
Issue number7
DOIs
Publication statusPublished - 2021 Jul 1

Keywords

  • asteriscane
  • seiridiasteriscane
  • semipinacol rearrangement

ASJC Scopus subject areas

  • Biotechnology
  • Analytical Chemistry
  • Biochemistry
  • Applied Microbiology and Biotechnology
  • Molecular Biology
  • Organic Chemistry

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