Journal
JOURNAL OF ANTIBIOTICS
Volume 70, Issue 5, Pages 632-638Publisher
JAPAN ANTIBIOTICS RESEARCH ASSOC
DOI: 10.1038/ja.2017.27
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Funding
- Ministry of Education, Culture, Sports, Science and Technology, Japan (JSPS KAKENHI) [JP15H01835, JP16H03277, JP16H06446, JP10F00032]
- Grants-in-Aid for Scientific Research [16H06446, 16H03277] Funding Source: KAKEN
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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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