期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 36, 页码 12688-12695出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201906753
关键词
enzyme-mimicking systems; host-guest systems; resorcinarene capsules; supramolecular catalysis; terpene cyclization
资金
- European Research Council [714620-TERPENECAT]
- Swiss National Science Foundation, NCCR Molecular Systems Engineering
- Bayerische Akademie der Wissenschaften (Junges Kolleg)
- Fundamental Research Funds for the Central Universities
The synthesis of terpene natural products remains a challenging task due to the enormous structural diversity in this class of compounds. Synthetic catalysts are unable to reproduce the tail-to-head terpene cyclization of cyclase enzymes, which create this diversity from just a few simple linear terpene substrates. Recently, supramolecular structures have emerged as promising enzyme mimetics. In the present study, the hexameric resorcinarene capsule was utilized as an artificial cyclase to catalyze the cyclization of sesquiterpenes. With the cyclization reaction as the key step, the first total synthesis of the sesquiterpene natural product delta-selinene was achieved. This represents the first total synthesis of a sesquiterpene natural product that is based on the cyclization of a linear terpene precursor inside a supramolecular catalyst. To elucidate the reaction mechanism, detailed kinetic studies and kinetic isotope measurements were performed. Surprisingly, the obtained kinetic data indicated that a rate-limiting encapsulation step is operational in the cyclization of sesquiterpenes.
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