title: Astellifadiene: Structure Determination by NMR Spectroscopy and Crystalline Sponge Method, and Elucidation of its Biosynthesis.
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.
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
authors.forename: Yudai
authors.initials: Y
authors.lastname: Matsuda
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
authors.forename: Takaaki
authors.initials: T
authors.lastname: Mitsuhashi
authors.affiliation: Graduate School of Engineering, The University of Tokyo, JST-ACCEL, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
authors.forename: Shoukou
authors.initials: S
authors.lastname: Lee
authors.affiliation: Graduate School of Engineering, The University of Tokyo, JST-ACCEL, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
authors.forename: Manabu
authors.initials: M
authors.lastname: Hoshino
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
authors.forename: Takahiro
authors.initials: T
authors.lastname: Mori
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Okada
authors.affiliation: RIKEN Center for Life Science Technologies, Yokohama, Kanagawa, 230-0045, Japan.
authors.forename: Huiping
authors.initials: H
authors.lastname: Zhang
authors.affiliation: RIKEN Center for Life Science Technologies, Yokohama, Kanagawa, 230-0045, Japan.
authors.forename: Fumiaki
authors.initials: F
authors.lastname: Hayashi
authors.affiliation: Graduate School of Engineering, The University of Tokyo, JST-ACCEL, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan. mfujita@appchem.t.u-tokyo.ac.jp.
authors.forename: Makoto
authors.initials: M
authors.lastname: Fujita
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan. abei@mol.f.u-tokyo.ac.jp.
authors.forename: Ikuro
authors.initials: I
authors.lastname: Abe
mesh_terms: D019883:Alkyl and Aryl Transferases / Q000378:metabolism; D001236:Aspergillus oryzae / Q000378:metabolism; D001688:Biological Products / Q000737:chemistry / Q000378:metabolism; D018360:Crystallography, X-Ray; D032842:Emericella / Q000737:chemistry / Q000378:metabolism; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D054830:Sesterterpenes / Q000096:biosynthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D001688:Biological Products; D054830:Sesterterpenes; D019883:Alkyl and Aryl Transferases; C108877:terpene synthase
keywords: biosynthesis; crystal growth; natural products; structure elucidation; terpenoids