Anion-π transaminase mimics. Issue 10 (3rd October 2017)

• Record Type: Journal Article
• Authors: Liu, Le; Matile, Stefan
• Is Part Of: Supramolecular chemistry. Volume 29:Issue 10(2017)
• Page Start: 702
• Page End: 706
• Publication Date: 2017-10-03
• Subjects: Anion-π interactions -- catalysis -- anionic transition states -- transamination -- imine isomerisation -- transaminase mimics -- pyridoxalphosphate -- rate enhancement -- stereoselectivity -- naphthalenediimides; Macromolecules -- Periodicals; Supramolecular chemistry -- Periodicals; 547.005
• DOI: 10.1080/10610278.2016.1258118
• Languages: English
• ISSNs: 1061-0278

Abstract

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. Abstract :