Arnold, Andreas M. M. and Dullinger, Philipp and Biswas, Aniruddha and Jandl, Christian and Horinek, Dominik and Gulder, Tanja (2023) Enzyme-like polyene cyclizations catalyzed by dynamic, self-assembled, supramolecular fluoro alcohol-amine clusters. NATURE COMMUNICATIONS, 14 (1): 813. ISSN , 2041-1723
Full text not available from this repository. (Request a copy)Abstract
Terpene cyclases enable the synthesis of (poly)cyclic carbon frameworks via ring closure of linear polyenes. Here, the authors report in-situ formed fluorinated-alcohol-amine supramolecular clusters that mimic terpene cyclases for shape-controlled polyene cyclizations. Terpene cyclases catalyze one of the most powerful transformations with respect to efficiency and selectivity in natural product (bio)synthesis. In such polyene cyclizations, structurally highly complex carbon scaffolds are built by the controlled ring closure of linear polyenes. Thereby, multiple C,C bonds and stereocenters are simultaneously created with high precision. Structural pre-organization of the substrate carbon chain inside the active center of the enzyme is responsible for the product- and stereoselectivity of this cyclization. Here, we show that in-situ formed fluorinated-alcohol-amine supramolecular clusters serve as artificial cyclases by triggering enzyme-like reactivity and selectivity by controlling substrate conformation in solution. Because of the dynamic nature of these supramolecular assemblies, a broad range of terpenes can be produced diastereoselectively. Mechanistic studies reveal a finely balanced interplay of fluorinated solvent, catalyst, and substrate as key to establishing nature's concept of a shape-selective polyene cyclization in organic synthesis.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | INTERNAL NUCLEOPHILIC TERMINATION; HEXAFLUOROISOPROPANOL HFIP; ASYMMETRIC CYCLIZATION; SYNTHETIC ACCESS; DITERPENES; LEWIS; TERPENES; ANALOGS; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry VI - Physical Chemistry (Solution Chemistry) > Prof. Dr. Dominik Horinek |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 23 Mar 2024 08:53 |
| Last Modified: | 23 Mar 2024 08:53 |
| URI: | https://pred.uni-regensburg.de/id/eprint/60302 |
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