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Scientific Article
unige:95403 
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Anion-π transaminase mimics |
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| 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 interactions — Catalysis — Anionic transition states — Transamination — Imine isomerisation — Transaminase mimics — Pyridoxalphosphate — Rate enhancement — Stereoselectivity — Naphthalenediimides | |
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Article (Published version) (882 Kb) - Limited access to UNIGE Article (Accepted version) (685 Kb) - Free access |
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| Structures | ||
| Research group | Groupe Matile | |
| 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 https://archive-ouverte.unige.ch/unige:95403 |
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