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Synthesis 2019; 51(11): 2305-2310
DOI: 10.1055/s-0037-1610867
paper
© Georg Thieme Verlag Stuttgart · New York

Bioinspired Synthesis of the Central Core of Halichonadin H: The Passerini Reaction in a Hypothetical Biosynthesis of Marine Natural Products

Yoshiyasu Ichikawa*
a   Faculty of Science, Kochi University, Akebono-cho, Kochi 780-8520, Japan   Email: ichikawa@kochi-u.ac.jp
,
Toshiki Yamasaki
a   Faculty of Science, Kochi University, Akebono-cho, Kochi 780-8520, Japan   Email: ichikawa@kochi-u.ac.jp
,
Keisuke Nakanishi
b   Department of Applied Chemistry, Faculty of Advanced Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555, Japan
,
Yutaro Udagawa
b   Department of Applied Chemistry, Faculty of Advanced Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555, Japan
,
Seijiro Hosokawa
b   Department of Applied Chemistry, Faculty of Advanced Science and Engineering, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555, Japan
,
Toshiya Masuda
c   Graduate School of Human Life Science, Osaka City University, Osaka 558-8585, Japan
› Author AffiliationsWe are grateful for the financial support provided by a Grant-in-Aid for Scientific Research (C) (16K01916) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT).
Further Information

Publication History

Received: 30 January 2019

Accepted after revision: 08 February 2019

Publication Date:
14 March 2019 (online)

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Abstract

A pathway is proposed for the biosynthesis of the unique homodimeric terpene, halichonadin H. The proposed biosynthetic pathway involves two key Passerini reactions of eudesmane-type terpene isocyanides. The Passerini reaction of a model terpene isocyanide and formaldehyde afforded an α-hydroxy acetamide, which was further subjected to oxidation and a second Passerini reaction. This reaction sequence furnished an α-hydroxy malonamide connected with two identical terpene units which is the identical structural motif found in halichonadin H.

Key words

marine natural products - terpenes - isocyanides - biosynthesis - Passerini reaction

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1610867.
  • Supporting Information
 

  • References

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