Theoretical Study on the Mechanism of Spirocyclization in Spiroviolene Biosynthesis

• Sato Hajime

  Graduate School of Pharmaceutical Sciences, The University of Tokyo Interdisciplinary Graduate School of Medicine and Engineering, University of Yamanashi

• Takagi Taisei

  Graduate School of Pharmaceutical Sciences, The University of Tokyo

• Miyamoto Kazunori

  Graduate School of Pharmaceutical Sciences, The University of Tokyo

• Uchiyama Masanobu

  Graduate School of Pharmaceutical Sciences, The University of Tokyo Research Initiative for Supra-Materials (RISM), Shinshu University

Abstract

Spiroviolene is a spirocyclic triquinane diterpene produced by Streptomyces violens. Recently, a biosynthetic pathway that includes secondary carbocation intermediates and a complicated concerted skeletal rearrangement was proposed for spiroviolene, based upon careful labeling experiments. On the basis of density functional theory (DFT) calculations, we propose a revised pathway for spiroviolene biosynthesis, involving a multistep carbocation cascade that bypasses the formation of unstable secondary carbocations by breaking the adjacent C–C bond to form a more stable tertiary carbocation (IM3) and by Wagner–Meerwein 1,2-methyl rearrangement (IM7).

Journal

• Chemical and Pharmaceutical Bulletin

  Chemical and Pharmaceutical Bulletin 69 (10), 1034-1038, 2021-10-01

  The Pharmaceutical Society of Japan

Keywords

• terpene
• biosynthesis
• density functional theory
• carbocation

Details

• CRID: 1390852514694419456
• NII Article ID: 130008095539
• NII Book ID: AA00602100
• DOI: 10.1248/cpb.c21-00536
• ISSN: 13475223
• ISSN: 00092363
• NDL BIB ID: 031714225
• PubMed: 34602572
• Web Site: http://id.ndl.go.jp/bib/031714225
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I031714225
• Web Site: https://www.jstage.jst.go.jp/article/cpb/69/10/69_c21-00536/_pdf
• Text Lang: en
• Data Source:
  • JaLC
  • NDL
  • Crossref
  • PubMed
  • CiNii Articles
  • KAKEN
• Abstract License Flag: Disallowed