en
Scientific article
Open access
English

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

Published inAngewandte Chemie, vol. 55, no. 13, p. 4275-4279
Publication date2016
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.

Keywords
  • Anion–π interactions
  • Catalysis
  • Enolates
  • Preorganization
  • Selectivity
Research group
Citation (ISO format)
COTELLE, Yoann et al. Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces. In: Angewandte Chemie, 2016, vol. 55, n° 13, p. 4275–4279. doi: 10.1002/anie.201600831
Main files (2)
Article (Published version)
accessLevelRestricted
Article (Accepted version)
accessLevelPublic
Identifiers
ISSN of the journal1433-7851
584views
190downloads

Technical informations

Creation03/18/2016 9:15:00 AM
First validation03/18/2016 9:15:00 AM
Update time03/15/2023 12:13:35 AM
Status update03/15/2023 12:13:35 AM
Last indexation01/16/2024 8:28:46 PM
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack