Unified Total Synthesis of Stemoamide-Type Alkaloids by Chemoselective Assembly of Five-Membered Building Blocks

Amakoto Yoritate, Yoshito Takahashi, Hayato Tajima, Chisato Ogihara, Takashi Yokoyama, Yasuki Soda, Takeshi Oishi, Takaaki Sato, Noritaka Chida

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

A unified total synthesis of stemoamide-type alkaloids is reported. Our synthetic approach features the chemoselective convergent assembly of five-membered building blocks via stemoamide as the common precursor to tetracyclic natural products. The synthesis consists of two successive coupling reactions of the three five-membered building blocks. The first coupling reaction is the vinylogous Michael addition/reduction sequence, which enables the gram-scale synthesis of stemoamide. The second coupling reaction is a chemoselective nucleophilic addition to stemoamide. While the lactone-selective nucleophilic addition to stemoamide affords saxorumamide and isosaxorumamide, the lactam-selective reductive nucleophilic addition leads to the formation of stemonine. Both chemoselective nucleophilic additions enable direct modification of stemoamide, resulting in highly concise and efficient total syntheses of the stemoamide-type alkaloids.

Original languageEnglish
Pages (from-to)18386-18391
Number of pages6
JournalJournal of the American Chemical Society
Volume139
Issue number50
DOIs
Publication statusPublished - Dec 20 2017
Externally publishedYes

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Alkaloids
Lactams
Lactones
stemoamide
Biological Products

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Unified Total Synthesis of Stemoamide-Type Alkaloids by Chemoselective Assembly of Five-Membered Building Blocks. / Yoritate, Amakoto; Takahashi, Yoshito; Tajima, Hayato; Ogihara, Chisato; Yokoyama, Takashi; Soda, Yasuki; Oishi, Takeshi; Sato, Takaaki; Chida, Noritaka.

In: Journal of the American Chemical Society, Vol. 139, No. 50, 20.12.2017, p. 18386-18391.

Research output: Contribution to journalArticle

Yoritate, A, Takahashi, Y, Tajima, H, Ogihara, C, Yokoyama, T, Soda, Y, Oishi, T, Sato, T & Chida, N 2017, 'Unified Total Synthesis of Stemoamide-Type Alkaloids by Chemoselective Assembly of Five-Membered Building Blocks', Journal of the American Chemical Society, vol. 139, no. 50, pp. 18386-18391. https://doi.org/10.1021/jacs.7b10944
Yoritate, Amakoto ; Takahashi, Yoshito ; Tajima, Hayato ; Ogihara, Chisato ; Yokoyama, Takashi ; Soda, Yasuki ; Oishi, Takeshi ; Sato, Takaaki ; Chida, Noritaka. / Unified Total Synthesis of Stemoamide-Type Alkaloids by Chemoselective Assembly of Five-Membered Building Blocks. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 50. pp. 18386-18391.
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