Acid-Promoted Rearrangement of Drimane Type Epoxy Compounds and Their Application in Natural Product Synthesis

• Fujiwara Naoko

  School of Pharmaceutical Sciences, International University of Health and Welfare

• Kinoshita Masako

  Faculty of Pharmaceutical Sciences, Toho University

• Uchida Akira

  Faculty of Sciences, Toho University

• Ono Machiko

  School of Pharmaceutical Sciences, International University of Health and Welfare

• Kato Keisuke

  Faculty of Pharmaceutical Sciences, Toho University

• Akita Hiroyuki

  Faculty of Pharmaceutical Sciences, Toho University

Abstract

The reactions of (±)-α-epoxy drimenol (4) and (±)-α-epoxy drimenyl cyanide (6) with acids (proton acid or Lewis acid) selectively gave the rearranged aldehyde (±)-13 and (±)-15 having the hydroindane skeleton, respectively, while the reactions of (±)-4 and (±)-6 with Dibal-H selectively afforded the allyl alcohol (±)-14 and (±)-16, respectively. The reactions of (8aR)-6 and (8aS)-6 with Dibal-H were applied for the determination of the absolute structure of natural 7β-acetoxy-ent-labda-8(17),13(14)E-dien-15-ol (18). The reaction of (±)-α-epoxy bicyclofarnesol (5) and (8aS)-5 with proton acid selectively provided the rearranged ketol (±)- and (8aS)-31 having the hydroindane skeleton, respectively. The optically active (8aS)-31 was converted to the natural (9S)-austrodoric acid (33).

Journal

• Chemical and Pharmaceutical Bulletin

  Chemical and Pharmaceutical Bulletin 60 (4), 562-570, 2012

  The Pharmaceutical Society of Japan

Keywords

• α-epoxy drimenol
• α-epoxy bicyclofarnesol
• α-epoxy drimenyl cyanide
• (10<i>S</i>,7<i>R</i>)-7-acetoxy-labda-8(17),13(14)<i>E</i>-dien-15-ol
• (9<i>S</i>)-austrodoric acid
• acid-promoted rearrangement

Details

• CRID: 1390001204176659584
• NII Article ID: 130001852451
• NII Book ID: AA00602100
• DOI: 10.1248/cpb.60.562
• COI: 1:STN:280:DC%2BC38rhtlOjtw%3D%3D
• ISSN: 13475223
• ISSN: 00092363
• NDL BIB ID: 023533142
• PubMed: 22466743
• Web Site: http://id.ndl.go.jp/bib/023533142
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I023533142
• Web Site: https://www.jstage.jst.go.jp/article/cpb/60/4/60_4_562/_pdf
• Text Lang: en
• Data Source:
  • JaLC
  • NDL
  • Crossref
  • PubMed
  • CiNii Articles
  • KAKEN
• Abstract License Flag: Disallowed