期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 27, 期 38, 页码 9758-9762出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202101371
关键词
carbocations; DFT calculations; hydride shifts; isotopes; terpenes
资金
- DFG [DI1536/7-2]
- Projekt DEAL
The study shows that 1,3-hydride shifts are rare events in guaiane biosynthesis, and can only occur in a few stereoisomeric skeletons with well-defined stereochemistry. This was exemplified by the mechanism of guaia-4(15)-en-11-ol synthase from California poplar, which produces guaianes with unusual stereochemical properties. The general results from DFT calculations were confirmed experimentally through isotopic-labeling experiments with guaia-4(15)-en-11-ol synthase.
A systematic computational study addressing the entire chemical space of guaianes in conjunction with an analysis of all known compounds shows that 1,3-hydride shifts are rare events in guaiane biosynthesis. As demonstrated here, 1,3-hydride shifts towards guaianes can only be realized for two stereochemically well defined out of numerous possible stereoisomeric skeletons. One example is given by the mechanism of guaia-4(15)-en-11-ol synthase from California poplar, an enzyme that yields guaianes with unusual stereochemical properties. The general results from DFT calculations were experimentally verified through isotopic-labeling experiments with guaia-4(15)-en-11-ol synthase.
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