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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

Angewandte Chemie (International ed.), 2016-03, Vol.55 (13), p.4275-4279 [Periódico revisado por pares]

Germany: Blackwell Publishing Ltd

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  • Título:
    Anion-π Catalysis of Enolate Chemistry: Rigidified Leonard Turns as a General Motif to Run Reactions on Aromatic Surfaces
  • Autor: Cotelle, Yoann ; Benz, Sebastian ; Avestro, Alyssa-Jennifer ; Ward, Thomas R. ; Sakai, Naomi ; Matile, Stefan
  • Assuntos: anion-π interactions ; Anions ; Catalysis ; Chemical Sciences ; enolates ; Intermediates ; Organic chemistry ; preorganization ; Rigidity ; selectivity ; Substrates ; Thioesters
  • É parte de: Angewandte Chemie (International ed.), 2016-03, Vol.55 (13), p.4275-4279
  • Notas: Swiss NCCR
    European Research Council
    Swiss National Centre of Competence in Research
    Swiss SERI/FCS
    istex:F7BBDCA3FE04A982E16221FEC2925DC6E5DC6168
    ark:/67375/WNG-P49NJ4XG-Q
    ArticleID:ANIE201600831
    Swiss NSF
    These authors contributed equally to this work.
    ObjectType-Article-1
    SourceType-Scholarly Journals-1
    ObjectType-Feature-2
    content type line 23
  • Descrição: 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. Served on a platter: Simple, compact, and precisely sculpted Leonard turns are introduced to firmly and reliably place reactions on aromatic surfaces, minimizing entropic costs to maximize enthalpic gains. The significant change in selectivity (ηd/f) from less desirable decarboxylation with loose turns (right) to more relevant enolate addition pathways on π‐acidic surfaces with rigidified Leonard turns (left) demonstrates the power of this concept.
  • Editor: Germany: Blackwell Publishing Ltd
  • Idioma: Inglês
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  • Realização: ABCD-USP USP   Logos de Redes Sociais: Freepik

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