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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 |
Authors: | Grossmann, Oleg Browse this author | Maji, Rajat Browse this author | Aukland, Miles H. Browse this author | Lee, Sunggi Browse this author | List, Benjamin Browse this author →KAKEN DB |
Keywords: | Lewis acids | N-acyliminium ions | Mukaiyama-Mannich reaction | imidodiphosphorimidates | organocatalysis |
Issue Date: | 21-Feb-2022 |
Publisher: | Wiley-Blackwell |
Journal Title: | Angewandte chemie-international edition |
Volume: | 61 |
Issue: | 9 |
Start Page: | e202115036 |
Publisher DOI: | 10.1002/anie.202115036 |
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. |
Type: | article |
URI: | http://hdl.handle.net/2115/85413 |
Appears in Collections: | 化学反応創成研究拠点:ICReDD (Institute for Chemical Reaction Design and Discovery : ICReDD) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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