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Astellifadiene: Structure Determination by NMR Spectroscopy and Crystalline Sponge Method, and Elucidation of its Biosynthesis
Author(s) -
Matsuda Yudai,
Mitsuhashi Takaaki,
Lee Shoukou,
Hoshino Manabu,
Mori Takahiro,
Okada Masahiro,
Zhang Huiping,
Hayashi Fumiaki,
Fujita Makoto,
Abe Ikuro
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201601448
Subject(s) - sponge , chemistry , biosynthesis , aspergillus oryzae , terpene , stereochemistry , protonation , alkyl , nuclear magnetic resonance spectroscopy , absolute configuration , hydride , organic chemistry , enzyme , biology , hydrogen , ion , botany
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 .