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Eder, Johannes ; Antonov, Alexander S. ; Tupikina, E. Y. ; Gschwind, Ruth M.

Chiral Diselenophosphoric Acids for Ion Pair Catalysis: A Novel Approach to Enhance Both Proton Donating and Proton Accepting Properties

Eder, Johannes, Antonov, Alexander S. , Tupikina, E. Y. und 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.

Veröffentlichungsdatum dieses Volltextes: 22 Mai 2024 08:37
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.58291


Zusammenfassung

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 ...

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.



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftChemistry – A European Journal
Verlag:Wiley
Datum15 Mai 2024
InstitutionenChemie und Pharmazie > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind
Identifikationsnummer
WertTyp
10.1002/chem.202401793DOI
Stichwörter / KeywordsIon pair catalysis · NMR spectroscopy · Hydrogen bond · Organocatalysis · Selenium
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenZum Teil
URN der UB Regensburgurn:nbn:de:bvb:355-epub-582918
Dokumenten-ID58291

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