Astellifadiene: Structure Determination by NMR Spectroscopy and Crystalline Sponge Method, and Elucidation of its Biosynthesis. Issue 19 (1st April 2016)

• Record Type: Journal Article
• Authors: Matsuda, Yudai; Mitsuhashi, Takaaki; Lee, Shoukou; Hoshino, Manabu; Mori, Takahiro; Okada, Masahiro; Zhang, Huiping; Hayashi, Fumiaki; Fujita, Makoto; Abe, Ikuro
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 19(2016)
• Page Start: 5785
• Page End: 5788
• Publication Date: 2016-04-01
• Subjects: biosynthesis -- crystal growth -- natural products -- structure elucidation -- terpenoids; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201601448
• Languages: English
• ISSNs: 1433-7851

Abstract

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 of1 was initially investigated by extensive NMR analyses, and was further confirmed by the crystalline sponge method, which established the absolute structure of1 and demonstrated the usefulness of the method in the structure determination of complex hydrocarbon natural products. Furthermore, the biosynthesis of1 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 of1 . Abstract : 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 of1 was unambiguously determined by the crystalline sponge method coupled with NMR analyses. Further, the biosynthesis of1 was proposed on the basis of the isotope‐incorporation experiments performed both in vivo and in vitro.