Catalytic Asymmetric Additions of Enol Silanes to In Situ Generated Cyclic, Aliphatic N-Acyliminium Ions
- Title
- Catalytic Asymmetric Additions of Enol Silanes to In Situ Generated Cyclic, Aliphatic N-Acyliminium Ions
- Author(s)
- Grossmann, Oleg ; Maji, Rajat ; Aukland, Miles H. ; Lee, Sunggi ; List, Benjamin
- Issued Date
- 2022-02
- Citation
- Angewandte Chemie - International Edition, v.61, no.9
- Type
- Article
- Author Keywords
- Lewis acids ; N-acyliminium ions ; Mukaiyama-Mannich reaction ; imidodiphosphorimidates ; organocatalysis
- Keywords
- REISSERT-TYPE REACTION ; INTERMOLECULAR ADDITION ; GAS-PHASE ; CYCLIZATIONS ; ORGANOCATALYSIS ; HYDROXYLACTAMS ; ALDOLIZATIONS ; NUCLEOPHILES ; DIVERSITY ; CHEMISTRY
- ISSN
- 1433-7851
- Abstract
- Strong and confined imidodiphosphorimidate (IDPi) catalysts enable highly enantioselective substitutions of cyclic, aliphatic hemiaminal ethers with enol silanes. 2-Substituted pyrrolidines, piperidines, and azepanes are obtained with high enantioselectivities, and the method displays a broad tolerance of various enol silane nucleophiles. Several natural products can be accessed using this methodology. Mechanistic studies support the intermediacy of non-stabilized, cyclic N-(exo-acyl)iminium ions, paired with the confined chiral counteranion. Computational studies suggest transition states that explain the observed enantioselectivity. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
- Publisher
- John Wiley & Sons Ltd.
- Related Researcher
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Lee, Sunggi
- Research Interests Organic synthesis; Catalyst development; Reaction development; Radical chemistry; Stereoselective reaction
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- Appears in Collections:
- Department of Physics and Chemistry Organic Synthesis & Catalysis Lab 1. Journal Articles
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