Affiliation:
1. Kekulé-Institute for Organic Chemistry and Biochemistry University of Bonn Gerhard-Domagk-Straße 1 53121 Bonn Germany
2. Department for Chemistry University of Cologne Greinstraße 4 50939 Cologne Germany
3. Institute for Inorganic Chemistry University of Bonn Gerhard-Domagk-Straße 1 53121 Bonn Germany
Abstract
AbstractMining of a terpene synthase from Streptomyces subrutilus resulted in the identification of the hexacyclic sesterterpene subrutilane, besides eight pentacyclic side products. Subrutilane represents the first case of a saturated sesterterpene hydrocarbon. Its structure, including the absolute configuration, was unambiguously determined through X‐ray crystallographic analysis and stereoselective deuteration. The cyclisation mechanism to subrutilane and its side products was investigated in all detail by isotopic labelling experiments and DFT calculations. The subrutilane synthase (SrS) also converted (2Z)‐GFPP into one major product. Additional compounds were obtained from the substrate analogues (7R)‐6,7‐dihydro‐GFPP and (2Z,7R)‐6,7‐dihydro‐GFPP with blocked reactivity at the C6−C7 bond. Interestingly, the early steps of the cyclisation cascade with (2Z)‐GFPP and the saturated substrate analogues were analogous to those of GFPP, but then deviations from the natural cyclisation mode occur.
Funder
Deutsche Forschungsgemeinschaft
Subject
General Chemistry,Catalysis
Cited by
2 articles.
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