UNIGE document Scientific Article
previous document  unige:94491  next document
add to browser collection
Title

Electric-Field-Assisted Anion−π Catalysis

Authors
Published in Journal of the American Chemical Society. 2017, vol. 139, no. 19, p. 6558-6561
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.
Identifiers
Full text
Article (Published version) (680 Kb) - document accessible for UNIGE members only Limited access to UNIGE
Other version: http://pubs.acs.org/doi/abs/10.1021/jacs.7b02421
Structures
Research group Groupe Matile
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. https://archive-ouverte.unige.ch/unige:94491

23 hits

0 download

Update

Deposited on : 2017-05-24

Export document
Format :
Citation style :