科研之友
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摘要
The possibility to stabilise anionic transition states on -acidic aromatic surfaces has been explicitly demonstrated first in 2013. Since then, anion- catalysis has been introduced to asymmetric enamine and iminium chemistry and to cascade processes, and the first anion- enzyme has been created. Moving beyond systems that operate with nitronate- interactions, this report adds transamination to the repertoire of anion- 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 -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- interactions with 2-azaallyl anion intermediates catalyse the isomerisation of trifluoromethylimines by cumulative asymmetric umpolung on -acidic surfaces. [GRAPHICS]
- 出版日期2017
