Silver‐Catalyzed Enantioselective Sulfimidation Mediated by Hydrogen Bonding Interactions
| Autor: | Stefan M. Huber, Rajasekar Reddy Annapureddy, Christian Merten, Tino P. Golub, Finn Burg, Thorsten Bach, Johannes Gramüller |
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| Rok vydání: | 2021 |
| Předmět: |
ligand design
Hydrogen bond Chemistry Phenanthroline Nitrene Chiral ligand Enantioselective synthesis asymmetric catalysis General Chemistry Asymmetric Catalysis | Hot Paper General Medicine Combinatorial chemistry Catalysis Kinetic resolution ddc chemistry.chemical_compound enantioselectivity hydrogen bonds Molecule silver Enantiomeric excess Research Articles Research Article |
| Zdroj: | Angewandte Chemie (International Ed. in English) |
| ISSN: | 1521-3757 0044-8249 |
| DOI: | 10.1002/ange.202016561 |
| Popis: | An enantioselective sulfimidation of 3‐thiosubstituted 2‐quinolones and 2‐pyridones was achieved with a stoichiometric nitrene source (PhI=NNs) and a silver‐based catalyst system. Key to the success of the reaction is the use of a chiral phenanthroline ligand with a hydrogen bonding site. The enantioselectivity does not depend on the size of the two substituents at the sulfur atom but only on the binding properties of the heterocyclic lactams. A total of 21 chiral sulfimides were obtained in high yields (44–99 %) and with significant enantiomeric excess (70–99 % ee). The sulfimidation proceeds with high site‐selectivity and can also be employed for the kinetic resolution of chiral sulfoxides. Mechanistic evidence suggests the intermediacy of a heteroleptic silver complex, in which the silver atom is bound to one molecule of the chiral ligand and one molecule of an achiral 1,10‐phenanthroline. Support for the suggested reaction course was obtained by ESI mass spectrometry, DFT calculations, and a Hammett analysis. A picky ligand: A chiral phenanthroline ligand allows for the site‐ and enantioselective imidation (Ns=para‐nitrosulfonyl) of a variety of sulfides. Silver acts in concert with an achiral 1,10‐phenanthroline (1,10‐phen) ligand as the catalytically active center. |
| Databáze: | OpenAIRE |
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