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Electric-Field-Assisted Anion−π Catalysis

Published inJournal of the American Chemical Society, vol. 139, no. 19, p. 6558-6561
Publication date2017
Abstract

This report focuses on the remote control of anion−π catalysis by electric fields. We have synthesized and immobilized anion−π catalysts to explore the addition reaction of malonic acid half thioesters to enolate acceptors on conductive indium tin oxide surfaces. Exposed to increasing electric fields, anion−π catalysts show an increase in activity and an inversion of selectivity. These changes originate from a more than 100-fold rate enhancement of the disfavored enolate addition reaction that coincides with an increase in selectivity of transition-state recognition by up to −14.8 kJ mol–1. The addition of nitrate with strong π affinity nullified (IC50 = 2.2 mM) the responsiveness of anion−π catalysts to electric fields. These results support that the polarization of the π-acidic naphthalenediimide surface in anion−π catalysts with electric fields increases the recognition of anionic intermediates and transition states on this polarized π surface, that is, the existence and relevance of electric-field-assisted anion−π catalysis.

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Citation (ISO format)
AKAMATSU, Masaaki, SAKAI, Naomi, MATILE, Stefan. Electric-Field-Assisted Anion−π Catalysis. In: Journal of the American Chemical Society, 2017, vol. 139, n° 19, p. 6558–6561. doi: 10.1021/jacs.7b02421
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ISSN of the journal0002-7863
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Creation05/23/2017 1:46:00 PM
First validation05/23/2017 1:46:00 PM
Update time03/15/2023 1:43:05 AM
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