P-33 Synthetic Study on Yuzurimine-type Alkaloids

DOI
  • Hayakawa Ichiro
    Graduate School of Natural Science and Technology, Okayama University
  • Ikeda Masaki
    Graduate School of Natural Science and Technology, Okayama University
  • Niida Keisuke
    Graduate School of Pure and Applied Sciences, University of Tsukuba
  • Nakashige Yuichi
    Graduate School of Natural Science and Technology, Okayama University
  • Nagayasu Anna
    Graduate School of Natural Science and Technology, Okayama University
  • Nomura Saki
    Graduate School of Natural Science and Technology, Okayama University
  • Saito Keita
    Graduate School of Pure and Applied Sciences, University of Tsukuba
  • Kigoshi Hideo
    Graduate School of Pure and Applied Sciences, University of Tsukuba
  • Sakakura Akira
    Graduate School of Natural Science and Technology, Okayama University

Bibliographic Information

Other Title
  • P-33 ユズリハアルカロイド・ユズリミン類の合成研究

Abstract

Yuzurimine-type alkaloids make up a sub-family of Daphniphyllum alkaloids isolated from Daphniphyllum macropodum by Hirata and co-workers. The structural feature of yuzurimine-type alkaloids is the [6-7-5-5] tetracarbocyclic core framework fused with an indolizidine unit. In this presentation, we describe our construction of the [6-7-5-5] tetracarbocyclic core, all the carbocyclic framework of yuzurimine-type alkaloids by using unique in situ intramolecular Wittig reaction and Sm-mediated cyclization as key steps. A plausible reaction pathway for the formation of the seven-membered enone 27 via intramolecular Wittig reaction can be explained as follows. Alkylation of iodide 23 with (methoxycarbonylmethylene)tributylphosphorane (15) followed by deprotonation with an excess of phosphorane 15 might afforded ylide 25. Ylide 25 was then cyclized by intramolecular Wittig reaction to afford seven-membered enone 27. Enone 27 was converted into aldehyde 28, which was treated with SmCl2 to afford lactone 29 and tetracyclic compound 30. These compounds 29 and 30 contain the [6-7-5-5] tetracarbocyclic cores of yuzurimine-type alkaloids. Also, we attempted to the construction of the heterocyclic portion of yuzurimine-type alkaloids by using Staudinger reaction, aza-Wittig reaction, and intramolecular SN2 reaction as key steps.

Journal

Details 詳細情報について

  • CRID
    1390285697597620736
  • NII Article ID
    130007906327
  • DOI
    10.24496/tennenyuki.59.0_375
  • ISSN
    24331856
  • Text Lang
    ja
  • Data Source
    • JaLC
    • CiNii Articles
  • Abstract License Flag
    Disallowed

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