学術雑誌論文 Cyclization mechanism of phomopsene synthase : mass spectrometry based analysis of various site-specifically labeled terpenes

Shinde, Sandip S.  ,  Minami, Atsushi  ,  Chen, Zhi  ,  Tokiwano, Tetsuo  ,  Toyomasu, Tomonobu  ,  Kato, Nobuo  ,  Sassa, Takeshi  ,  Oikawa, Hideaki

70 ( 5 )  , pp.632 - 638 , 2017-05 , 日本抗生物質学術協議会(Japan Antibiotics Research Association)
ISSN:0021-8820
内容記述
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.
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https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/67522/3/16JA-phomopsene_Final-626.pdf

https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/67522/2/Supporting%20Information.docx

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