33 酵素的手法による光学活性ビシクロ[3.3.0]オクタン化合物の合成とその天然物合成への応用(口頭発表の部)

• 井上 武久

  京都薬大

• 荒木 守

  京都薬大

• 細見 光一

  京都薬大

• 岡本 健

  京都薬大

• 野出 學

  京都薬大

書誌事項

タイトル別名

• 33 Preparation of Chiral Bicyclo[3.3.0]octanes by Enzymatic Methods and Their Application to the Natural Products Syntheses

抄録

Chiral bicyclo[3.3.0]octane derivatives 1 are useful as chiral synthons for efficient synthesis of cyclic natural products. Here we describe the asymmetric transformation using enzymatic method of δ-symmetric bicyclic diketones 2a-c and tetraester 9, and the application of chiral bicyclo[3.3.0]octane derivatives [(+)-3b, (+)- and (-)-11] to natural products syntheses. 1. Baker's yeast-mediated asymmetric reduction of δ-symmetric bicyclic diketones 2a-c afforded the optical active ketols 3a-d in excellent enantioselectivity. Especially, ketol (+)-3b was the chiral intermediate for the total syntheses of (-)-cantabrenonic acids. Furthermore, usefulness of (+)-3b as a chiral bicyclic synthon was revealed by the short transformation of the ketol to the chiral intermediate (+)-4 in (+)-capnellenols syntheses (Scheme 5). 2. PPL-mediated asymmetric demethoxycarbonylation of achiral tetraester 9 obtained by Weiss reaction afforded the chiral triester (+)-10 in 98.3 %ee. The chiral triester was selectively demethoxycarbonylated to prepare chiral C_2-symmetry diester (+)-11. On the other hand, lipase AY-mediated asymmetric demethoxycarbonylation of achiral tetraester 9 directly afforded the chiral C_2-symmetry diester (-)-11 (100 %ee), having opposite chirality compared to the reaction with PPL. The results of lipase-mediated asymmetric transformation of achiral tetraester 9 are shown in Table 1. The chiral diesters (+)- and (-)-11 were very useful as chiral C_2-symmetry synthons for the total syntheses of (+)-carbacyclin, (-)-isoiridomyrmecin, (-)-ajmalicine (Scheme 7, 8, and 9).

収録刊行物

• 天然有機化合物討論会講演要旨集

  天然有機化合物討論会講演要旨集 36 (0), 250-257, 1994

  天然有機化合物討論会実行委員会

詳細情報

• CRID: 1390282681054761984
• NII論文ID: 110006679298
• DOI: 10.24496/tennenyuki.36.0_250
• ISSN: 24331856
• 本文言語コード: ja
• データソース種別:
  • JaLC
  • CiNii Articles
• 抄録ライセンスフラグ: 使用不可