en
Scientific article
Open access
English

Anion-π transaminase mimics

ContributorsLiu, Le; Matile, Stefan
Published inSupramolecular chemistry, vol. 29, no. 10, p. 702-706
Publication date2017
Abstract

The possibility to stabilise anionic transition states on π-acidic aromatic surfaces has been explicitly demonstrated first in 2013. Since then, anion-π catalysis has been introduced to asymmetric enamine and iminium chemistry and to cascade processes, and the first anion-π enzyme has been created. Moving beyond systems that operate with nitronate-π interactions, this report adds transamination to the repertoire of anion-π catalysis. Whereas bioinspired approaches to transamination with pyridoxalphosphate appeared less obvious in this context, the base-catalyzed isomerisation of trifluoromethylimines contains suitable anionic transition states. Run on increasingly π-acidic aromatic surfaces in covalent and supramolecular trifunctional systems, we find that both rate and enantioselectivity of this reaction increase. These results support that anion-π interactions with 2-azaallyl anion intermediates catalyse the isomerisation of trifluoromethylimines by cumulative asymmetric umpolung on π-acidic surfaces.

Keywords
  • Anion-π interactions
  • Catalysis
  • Anionic transition states
  • Transamination
  • Imine isomerisation
  • Transaminase mimics
  • Pyridoxalphosphate
  • Rate enhancement
  • Stereoselectivity
  • Naphthalenediimides
Research group
Citation (ISO format)
LIU, Le, MATILE, Stefan. Anion-π transaminase mimics. In: Supramolecular chemistry, 2017, vol. 29, n° 10, p. 702–706. doi: 10.1080/10610278.2016.1258118
Main files (2)
Article (Published version)
accessLevelRestricted
Article (Accepted version)
accessLevelPublic
Identifiers
ISSN of the journal1026-7816
442views
148downloads

Technical informations

Creation07/11/2017 11:27:00 AM
First validation07/11/2017 11:27:00 AM
Update time03/15/2023 1:49:46 AM
Status update03/15/2023 1:49:45 AM
Last indexation01/17/2024 12:16:45 AM
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack