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

Oleg Grossmann, Rajat Maji, Miles H. Aukland, Sunggi Lee, Benjamin List

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16 Scopus citations

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.

Original languageEnglish
Article numbere202115036
JournalAngewandte Chemie - International Edition
Volume61
Issue number9
DOIs
StatePublished - 21 Feb 2022

Bibliographical note

Publisher Copyright:
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Keywords

  • Lewis acids
  • Mukaiyama–Mannich reaction
  • N-acyliminium ions
  • imidodiphosphorimidates
  • organocatalysis

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