UNIGE document Scientific Article
previous document  unige:107049  next document
add to browser collection
Title

Remote Control of Anion-π Catalysis on Fullerene-Centered Catalytic Triads

Authors
Bauzá, Antonio
Frontera, Antonio
Published in Angewandte Chemie: International Edition. 2018, vol. 57, no. 34, p. 10883-10887
Abstract The design, synthesis and evaluation of catalytic triads composed of a central C60 fullerene with an amine base on one side and polarizability enhancers on the other side are reported. According to an enolate addition benchmark reaction, fullerene–fullerene–amine triads display the highest selectivity in anion–π catalysis observed so far, whereas NDI–fullerene–amine triads are not much better than fullerene–amine controls (NDI=naphthalenediimide). These large differences in activity are in conflict with the small differences in intrinsic π acidity, that is, LUMO energy levels and π holes on the central fullerene. However, they are in agreement with the high polarizability of fullerene–fullerene–amine triads. Activation and deactivation of the fullerene‐centered triads by intercalators and computational data on anion binding further indicate that for functional relevance, intrinsic π acidity is less important than induced π acidity, that is, the size of the oriented macrodipole of polarizable π systems that emerges only in response to the interaction with anions and anionic transition states. The resulting transformation is thus self‐induced, the anionic intermediates and transition states create their own anion–π catalyst.
Keywords Anion–π catalysisFullerenesInduced π acidityPolarizability
Identifiers
Full text
Structures
Research group Groupe Matile
Citation
(ISO format)
LOPEZ ANDARIAS, Javier et al. Remote Control of Anion-π Catalysis on Fullerene-Centered Catalytic Triads. In: Angewandte Chemie: International Edition, 2018, vol. 57, n° 34, p. 10883-10887. https://archive-ouverte.unige.ch/unige:107049

19 hits

5 downloads

Update

Deposited on : 2018-08-15

Export document
Format :
Citation style :