Eder, Johannes and Antonov, Alexander S. and Tupikina, Elena Yu. and Gschwind, Ruth M. (2024) Chiral Diselenophosphoric Acids for Ion Pair Catalysis: A Novel Approach to Enhance Both Proton Donating and Proton Accepting Properties. CHEMISTRY-A EUROPEAN JOURNAL, 30 (44). e202401793. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
The activation of poorly reactive substrates via strong chiral acids is a central topic in asymmetric ion pair catalysis these days. Despite highly successful scaffolds such as N-triflylphosphoramides, these catalysts either lack C2-symmetry or provide multiple H-bond acceptor sites, leading to lower ee values for certain reactions. We present BINOL-based diselenophosphoric acids (DSA) as an extremely promising alternative. Using an intertwined approach of synthesis and NMR studies, we developed a synthetic approach to DSA with up to 98 % NMR yield. The obtained acids provide both very high proton donor and proton acceptor properties, a bifunctionality, which is key to catalytic applications. Indeed, first reactivity test proved the much higher acidity of DSA and its ability to initiate Mukaiyama-Mannich reaction and protodesilylation of silyl ethers. Together with their C2-symmetry, the single donor and single acceptor situation, the decreased tendency of self-association, and the straightforward synthesis with potential 3,3'-substitution, the DSA provide all features ideal for the further development of ion pair catalysis. We present the first BINOL-based diselenophosphoric acids (DSA) obtained with up to 98 % NMR yield. DSA provide both very high proton donor and proton acceptor properties. Together with their C2-symmetry, the single donor and single acceptor situation, the decreased tendency of self-association, and the straightforward synthesis with potential 3,3'-substitution, the DSA provide all features ideal for the further development of ion pair catalysis. image
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CRYSTAL-STRUCTURE; BRONSTED ACID; ASYMMETRIC ORGANOCATALYSIS; TRANSFER HYDROGENATION; ALCOHOLS; BONDS; SALTS; MODE; P-31; H-1; Ion pair catalysis; NMR spectroscopy; Hydrogen bond; Organocatalysis; Selenium |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 Jan 2026 05:37 |
| Last Modified: | 14 Jan 2026 05:37 |
| URI: | https://pred.uni-regensburg.de/id/eprint/63889 |
Actions (login required)
 |
View Item |
