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Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Tool to Run Reactions on Aromatic Surfaces

Cotelle, Yoann and Benz, Sebastian and Avestro, Alyssa-Jennifer and Ward, Thomas R. and Sakai, Naomi and Matile, Stefan. (2016) Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Tool to Run Reactions on Aromatic Surfaces. Angewandte Chemie International Edition, 128 (13). pp. 4347-4351.

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Official URL: http://edoc.unibas.ch/53299/

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Abstract

To integrate anion–π, cation–π, and ion pair–π interactions in catalysis, the fundamental challenge is to run reactions reliably on aromatic surfaces. Addressing a specific question concerning enolate addition to nitroolefins, this study elaborates on Leonard turns to tackle this problem in a general manner. Increasingly refined turns are constructed to position malonate half thioesters as close as possible on π-acidic surfaces. The resulting preorganization of reactive intermediates is shown to support the disfavored addition to enolate acceptors to an absolutely unexpected extent. This decisive impact on anion–π catalysis increases with the rigidity of the turns. The new, rigidified Leonard turns are most effective with weak anion–π interactions, whereas stronger interactions do not require such ideal substrate positioning to operate well. The stunning simplicity of the motif and its surprisingly strong relevance for function should render the introduced approach generally useful.
Faculties and Departments:05 Faculty of Science > Departement Chemie
05 Faculty of Science > Departement Chemie > Chemie > Bioanorganische Chemie (Ward)
UniBasel Contributors:Ward, Thomas R. and Matile, Stefan
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Wiley
ISSN:1433-7851
e-ISSN:1521-3773
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:25 Jan 2017 15:25
Deposited On:25 Jan 2017 15:25

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