Astellifadiene : Structure Determination by NMR Spectroscopy and Crystalline Sponge Method, and Elucidation of its Biosynthesis

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

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Author(s)

  • Takaaki Mitsuhashi
  • Shoukou Lee
  • Manabu Hoshino
  • Takahiro Mori
  • Masahiro Okada
  • Huiping Zhang
  • Fumiaki Hayashi
  • Makoto Fujita
  • Ikuro Abe

Detail(s)

Original languageEnglish
Pages (from-to)5785-5788
Journal / PublicationAngewandte Chemie - International Edition
Volume55
Issue number19
Online published1 Apr 2016
Publication statusPublished - 4 May 2016
Externally publishedYes

Abstract

Genome mining of a terpene synthase gene from Emericella variecolor NBRC 32302 and its functional expression in Aspergillus oryzae led to the production of the new sesterterpene hydrocarbon, astellifadiene (1), having a 6-8-6-5-fused ring system. The structure of 1 was initially investigated by extensive NMR analyses, and was further confirmed by the crystalline sponge method, which established the absolute structure of 1 and demonstrated the usefulness of the method in the structure determination of complex hydrocarbon natural products. Furthermore, the biosynthesis of 1 was proposed on the basis of isotope-incorporation experiments performed both in vivo and in vitro. The cyclization of GFPP involves a protonation-initiated second cyclization sequence, 1,2-alkyl migration, and 1,5-hydride shift to generate the novel scaffold of 1. A unique tetracyclic fungal sesterterpene: Genome mining and heterologous expression of a cryptic fungal terpene synthase provided astellifadiene (1) with an unprecedented 6-8-6-5-fused ring system. The structure of 1 was unambiguously determined by the crystalline sponge method coupled with NMR analyses. Further, the biosynthesis of 1 was proposed on the basis of the isotope-incorporation experiments performed both in vivo and in vitro.

Research Area(s)

  • biosynthesis, crystal growth, natural products, structure elucidation, terpenoids

Citation Format(s)

Astellifadiene: Structure Determination by NMR Spectroscopy and Crystalline Sponge Method, and Elucidation of its Biosynthesis. / Matsuda, Yudai; Mitsuhashi, Takaaki; Lee, Shoukou et al.
In: Angewandte Chemie - International Edition, Vol. 55, No. 19, 04.05.2016, p. 5785-5788.

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review