Catalytic Asymmetric Additions of Enol Silanes to In Situ Generated Cyclic, Aliphatic N‐Acyliminium Ions

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 tolera...

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Autores principales: Grossmann, Oleg, Maji, Rajat, Aukland, Miles H., Lee, Sunggi, List, Benjamin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9303265/
https://www.ncbi.nlm.nih.gov/pubmed/34897932
http://dx.doi.org/10.1002/anie.202115036
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author Grossmann, Oleg
Maji, Rajat
Aukland, Miles H.
Lee, Sunggi
List, Benjamin
author_facet Grossmann, Oleg
Maji, Rajat
Aukland, Miles H.
Lee, Sunggi
List, Benjamin
author_sort Grossmann, Oleg
collection PubMed
description 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.
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spelling pubmed-93032652022-07-22 Catalytic Asymmetric Additions of Enol Silanes to In Situ Generated Cyclic, Aliphatic N‐Acyliminium Ions Grossmann, Oleg Maji, Rajat Aukland, Miles H. Lee, Sunggi List, Benjamin Angew Chem Int Ed Engl Communications 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. John Wiley and Sons Inc. 2022-01-12 2022-02-21 /pmc/articles/PMC9303265/ /pubmed/34897932 http://dx.doi.org/10.1002/anie.202115036 Text en © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ (https://creativecommons.org/licenses/by-nc/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
spellingShingle Communications
Grossmann, Oleg
Maji, Rajat
Aukland, Miles H.
Lee, Sunggi
List, Benjamin
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
title_full Catalytic Asymmetric Additions of Enol Silanes to In Situ Generated Cyclic, Aliphatic N‐Acyliminium Ions
title_fullStr Catalytic Asymmetric Additions of Enol Silanes to In Situ Generated Cyclic, Aliphatic N‐Acyliminium Ions
title_full_unstemmed Catalytic Asymmetric Additions of Enol Silanes to In Situ Generated Cyclic, Aliphatic N‐Acyliminium Ions
title_short Catalytic Asymmetric Additions of Enol Silanes to In Situ Generated Cyclic, Aliphatic N‐Acyliminium Ions
title_sort catalytic asymmetric additions of enol silanes to in situ generated cyclic, aliphatic n‐acyliminium ions
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9303265/
https://www.ncbi.nlm.nih.gov/pubmed/34897932
http://dx.doi.org/10.1002/anie.202115036
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