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Anion-π transaminase mimics

Published in Supramolecular chemistry. 2017, vol. 29, no. 10, p. 702-706
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 interactionsCatalysisAnionic transition statesTransaminationImine isomerisationTransaminase mimicsPyridoxalphosphateRate enhancementStereoselectivityNaphthalenediimides
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Research group Groupe Matile
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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 https://archive-ouverte.unige.ch/unige:95403

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Deposited on : 2017-07-12

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