Jansen, Dennis and Gramueller, Johannes and Niemeyer, Felix and Schaller, Torsten and Letzel, Matthias C. and Grimme, Stefan and Zhu, Hui and Gschwind, Ruth M. and Niemeyer, Jochen (2020) What is the role of acid-acid interactions in asymmetric phosphoric acid organocatalysis? A detailed mechanistic study using interlocked and non-interlocked catalysts. CHEMICAL SCIENCE, 11 (17). pp. 4381-4390. ISSN 2041-6520, 2041-6539
Full text not available from this repository. (Request a copy)Abstract
Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst-catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid-acid interactions have a drastic influence on the reaction rate and stereoselectivity of asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | GAUSSIAN-BASIS SETS; BRONSTED-ACID; TRANSFER HYDROGENATION; METHANOLYTIC DESYMMETRIZATION; BIFUNCTIONAL ORGANOCATALYST; CYCLIC ANHYDRIDES; SCREENING MODEL; REAL SOLVENTS; ATOMS; ENANTIOSELECTIVITY; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 24 Mar 2021 10:07 |
| Last Modified: | 24 Mar 2021 10:07 |
| URI: | https://pred.uni-regensburg.de/id/eprint/44593 |
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