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

Cotelle, Yoann; Benz, Sebastian; Avestro, Alyssa-Jennifer; Ward, Thomas R.; Sakai, Naomi; Matile, Stefan

doi:10.1002/anie.201600831

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Title		Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces
Authors		Cotelle, Yoann Benz, Sebastian Avestro, Alyssa-Jennifer Ward, Thomas R. Sakai, Naomi Matile, Stefan
Published in		Angewandte Chemie: International Edition. 2016, vol. 55, no. 13, p. 4275-4279
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
Identifiers		DOI: 10.1002/anie.201600831
Full text		Article (Published version) (1.6 MB) - Limited access to UNIGE Article (Accepted version) (3.1 MB) - Free access
Structures		Faculté des sciences / Section de chimie et biochimie / Département de chimie organique
Research group		Groupe Matile
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: International Edition, 2016, vol. 55, n° 13, p. 4275-4279. doi: 10.1002/anie.201600831 https://archive-ouverte.unige.ch/unige:81947