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Cyclization mechanism of phomopsene synthase : mass spectrometry based analysis of various site-specifically labeled terpenes

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Title: Cyclization mechanism of phomopsene synthase : mass spectrometry based analysis of various site-specifically labeled terpenes
Authors: Shinde, Sandip S. Browse this author
Minami, Atsushi Browse this author
Chen, Zhi Browse this author
Tokiwano, Tetsuo Browse this author
Toyomasu, Tomonobu Browse this author
Kato, Nobuo Browse this author
Sassa, Takeshi Browse this author
Oikawa, Hideaki Browse this author →KAKEN DB
Issue Date: May-2017
Publisher: 日本抗生物質学術協議会
Journal Title: Journal of antibiotics
Volume: 70
Issue: 5
Start Page: 632
End Page: 638
Publisher DOI: 10.1038/ja.2017.27
PMID: 28270685
Abstract: Elucidation of the cyclization mechanism catalyzed by terpene synthases is important for the rational engineering of terpene cyclases. We developed a chemoenzymatic method for the synthesis of systematically deuterium-labeled geranylgeranyl diphosphate ( GGPP), starting from site-specifically deuterium-labeled isopentenyl diphosphates (IPPs) using IPP isomerase and three prenyltransferases. We examined the cyclization mechanism of tetracyclic diterpene phomopsene with phomopsene synthase. A detailed EI-MS analysis of phomopsene labeled at various positions allowed us to propose the structures corresponding to the most intense peaks, and thus elucidate a cyclization mechanism involving double 1,2-alkyl shifts and a 1,2-hydride shift via a dolabelladien-15-yl cation. Our study demonstrated that this newly developed method is highly sensitive and provides sufficient information for a reliable assignment of the structures of fragmented ions.
Rights: Authors of original research articles are encouraged to submit the author's version of the accepted paper (the unedited manuscript) to their funding body's archive, for public release six months after publication. In addition, authors are encouraged to archive this version of the manuscript in their institution's repositories and on their personal websites, also six months after the original publication. This is in line with NPG's self-archiving policy.
Type: article (author version)
Appears in Collections:理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 及川 英秋

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