Asymmetric Total Synthesis of ent-Pyripyropene A

Shinichiro Fuse, Ayako Ikebe, Kazuya Oosumi, Tomoya Karasawa, Keisuke Matsumura, Miho Izumikawa, Kohei Johmoto, Hidehiro Uekusa, Kazuo Shin-Ya, Takayuki Doi, Takashi Takahashi

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

An asymmetric total synthesis of ent-pyripyropene A was achieved by a convergent synthetic route. We used our originally developed TiIII-catalyzed radical cyclization to construct an AB-ring portion that consisted of a trans-decalin skeleton with five contiguous stereogenic centers. The coupling between the AB-ring and the DE-ring portions, and a subsequent C-ring cyclization, led to the total synthesis of ent-pyripyropene A. An evaluation of the insecticidal activity of ent-pyripyropene A against two aphid species revealed that ent-pyripyropene A was 35-175 times less active than naturally occurring pyripyropene A. This result indicated that the biological target of pyripyropene A recognizes the absolute configuration of pyripyropene A. Radical chemistry! An asymmetric total synthesis of ent-pyripyropene A (see scheme) was achieved by a convergent synthetic route. Stereoselective synthesis of the AB-ring was achieved by the originally developed TiIII-catalyzed radical cyclization. An evaluation of insecticidal activity of ent-pyripyropene A against two aphid species revealed that ent-pyripyropene A was 35-175 times less active than naturally occurring pyripyropene A.

Original languageEnglish
Pages (from-to)9454-9460
Number of pages7
JournalChemistry - A European Journal
Volume21
Issue number26
DOIs
Publication statusPublished - 2015 Jun 1

Keywords

  • insecticidal activity
  • meroterpenoids
  • natural products
  • radical reactions
  • titanium

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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