Second-generation total synthesis of aplyronine A featuring Ni/Cr-mediated coupling reactions

Ichiro Hayakawa, Keita Saito, Sachiko Matsumoto, Shinichi Kobayashi, Ayaka Taniguchi, Kenichi Kobayashi, Yusuke Fujii, Takahiro Kaneko, Hideo Kigoshi

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Second-generation total synthesis of aplyronine A, a potent antitumor marine macrolide, was achieved using Ni/Cr-mediated coupling reactions as key steps. The overall yield of the second-generation synthetic pathway of aplyronine A was 1.4%, obtained in 38 steps based on the longest linear sequence. Compared to our first-generation synthetic pathway of aplyronine A, the second-generation synthesis greatly improved both the yield and number of steps. In particular, we improved the stereoselectivity in the construction of the C13 stereogenic center and the C14-C15 (E)-trisubstituted double bond using the asymmetric Ni/Cr-mediated coupling reaction. Furthermore, we established efficient reaction conditions for the asymmetric Ni/Cr-mediated coupling reaction between the C21-C28 segment and C29-C34 segment. Thus, this coupling reaction proceeded with an equimolar ratio of each segment.

Original languageEnglish
Pages (from-to)124-131
Number of pages8
JournalOrganic and Biomolecular Chemistry
Volume15
Issue number1
DOIs
Publication statusPublished - 2017

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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  • Cite this

    Hayakawa, I., Saito, K., Matsumoto, S., Kobayashi, S., Taniguchi, A., Kobayashi, K., Fujii, Y., Kaneko, T., & Kigoshi, H. (2017). Second-generation total synthesis of aplyronine A featuring Ni/Cr-mediated coupling reactions. Organic and Biomolecular Chemistry, 15(1), 124-131. https://doi.org/10.1039/c6ob02241c