Biomimetic Total Synthesis of (−)-Neroplofurol and (+)-Ekeberin D4 Triggered by Hydrolysis of Terminal Epoxides

• Takeshi Kodama

  Department of Chemistry, Graduate School of Science, Osaka City University

• Shingo Aoki

  Department of Chemistry, Graduate School of Science, Osaka City University

• Tomoki Matsuo

  Department of Chemistry, Graduate School of Science, Osaka City University

• Yoshimitsu Tachi

  Department of Chemistry, Graduate School of Science, Osaka City University

• Keisuke Nishikawa

  Department of Chemistry, Graduate School of Science, Osaka City University

• Yoshiki Morimoto

  Department of Chemistry, Graduate School of Science, Osaka City University

Abstract

To accumulate the chemical basis of epoxide-opening cascade biogenesis, chemical syntheses of sesqui- and triterpenoids were performed. The biomimetic total syntheses of (−)-neroplofurol (1) and (+)-ekeberin D4 (2) were accomplished by protic acid-catalyzed hydrolysis of the terminal epoxide from nerolidol diepoxide 3 and squalene tetraepoxide 4 through single and double 5-exo cyclizations in intermediates 5 and 6, respectively. This chemical reaction mimics the direct hydrolysis mechanism of epoxide hydrolases, enzymes that catalyze an epoxide-opening reaction to finally produce vicinal diols.

Journal

• Chemistry Letters

  Chemistry Letters 43 (10), 1662-1664, 2014-10

  Oxford University Press (OUP)

Keywords

• General Chemistry

Details

• CRID: 1360846644035710720
• NII Article ID: 130004693815
• DOI: 10.1246/cl.140618
• ISSN: 13480715
• ISSN: 03667022
• Web Site: https://academic.oup.com/chemlett/article-pdf/43/10/1662/55644378/cl.140618.pdf
• Data Source:
  • Crossref
  • CiNii Articles
  • KAKEN