Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Tool to Run Reactions on Aromatic Surfaces
JournalArticle (Originalarbeit in einer wissenschaftlichen Zeitschrift)
 
ID 3720505
Author(s) Cotelle, Yoann; Benz, Sebastian; Avestro, Alyssa-Jennifer; Ward, Thomas R.; Sakai, Naomi; Matile, Stefan
Author(s) at UniBasel Ward, Thomas R.
Matile, Stefan
Cotelle, Yoann
Year 2016
Year: comment 2016
Title Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Tool to Run Reactions on Aromatic Surfaces
Journal Angewandte Chemie International Edition
Volume 55
Number 13
Pages / Article-Number 4275-9
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.
Publisher Wiley
ISSN/ISBN 1433-7851 ; 1521-3773
edoc-URL http://edoc.unibas.ch/53299/
Full Text on edoc Available
Digital Object Identifier DOI 10.1002/ange.201600831
PubMed ID http://www.ncbi.nlm.nih.gov/pubmed/26916316
Document type (ISI) Journal Article
 
   

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