2017年5月1日
Cyclization mechanism of phomopsene synthase: Mass spectrometry based analysis of various site-specifically labeled terpenes
Journal of Antibiotics
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- 巻
- 70
- 号
- 5
- 開始ページ
- 632
- 終了ページ
- 638
- 記述言語
- 掲載種別
- 研究論文(学術雑誌)
- DOI
- 10.1038/ja.2017.27
© 2017 Japan Antibiotics Research Association All rights reserved. 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.
- リンク情報
- ID情報
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- DOI : 10.1038/ja.2017.27
- ISSN : 0021-8820
- eISSN : 1881-1469
- PubMed ID : 28270685
- SCOPUS ID : 85019599117