Enolate chemistry with anion–π interactions

Zhao, Yingjie; Sakai, Naomi; Matile, Stefan

doi:10.1038/ncomms4911

Cited by 74 publications

(76 citation statements)

References 46 publications

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“…The results summarized in Table 1 allow the following conclusions: 1) Most importantly, the triply substituted pyridinium tetrafluoroborates 6 d-g·BPh 4 indeed act as efficient catalysts for the alkylation of 1-chloroisochroman (1 a) and also of the acyclic chlorobenzyl ether 1 b, with all four of the silyl ketene acetals (2 a-d) tested (Table 1, entries 2-6, [8][9][10][11][13][14][15]. For the more reactive electrophile 1 a in combination with the silyl ketene acetal 2 a, catalyst loading as low as 2 mol % is sufficient to achieve full conversion within a few hours at À78 8C (entry 3).…”

Section: Methodsmentioning

confidence: 92%

“…Yet another mode of anion binding hinges on the interaction of anions with electron-poor p surfaces [8,9] a process for which Matile et al have recently reported first catalytic applications. [10,11] Our goal was to exploit electron-deficient pyridinium cations for anion-binding catalysis. [12] Our attention was drawn to pyridinium ions because their halide-binding ability is well documented, with regard to both structure [13] and complex stabilities.…”

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confidence: 99%

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Anion‐Binding Catalysis by Electron‐Deficient Pyridinium Cations

et al. 2014

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A new activation principle in organocatalysis is presented: halide binding through Coulombic interactions. This mode of catalysis was realized by using 3,5-di(carbomethoxy)pyridinium ions that carry an additional electron-withdrawing substituent on the nitrogen atom, for example, pentafluorobenzyl or cyanomethyl. For the N-pentafluorobenzyl derivative, Coulombic interaction with the pyridinium moiety is complemented in the solid state by anion-π interactions with the perfluorophenyl ring. Bromide and chloride are bound by these cations in a 1:1 stoichiometry. Catalysis of the C-C coupling between 1-chloroisochroman (and related electrophiles) with silyl ketene acetals occurs at -78 °C and at low catalyst loading (2 mol%).

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Section: Methodsmentioning

confidence: 92%

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confidence: 99%

Anion‐Binding Catalysis by Electron‐Deficient Pyridinium Cations

et al. 2014

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“…[103] The strength of anion-p interactions could be tuned by using p-acidic aromatic systems with high and positive quadrupole moment. Recently, Zhao et al [104] developed this idea to design new anion-p interaction organocatalyst which would be widely used in chemical and biological reactions. They used NDI (Q zz 5 119 B) and its analogues with electron withdrawing substituents with high positive quadrupole moment as strongest p-acid aromatics.…”

Section: Molecular Catalysts and Enzymesmentioning

confidence: 99%

Functional molecules and materials by π‐Interaction based quantum theoretical design

Tehrani

Kim

2016

Int J of Quantum Chemistry

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The intermolecular and intramolecular noncovalent interactions involving p-aromatic compounds have attracted increasing attention over the last decades in chemistry, biology and material sciences. In this review, we discuss contemporary computational studies on the nature and strength of H-p, p-p, and anion-p interactions. We emphasize how modern quantum theoretical approaches ahead of experiment can provide insight into the design of new materials and devices by tuning the p-interactions in cooperative and competitive manners. Usefulness of such approaches towards designing new materials is demonstrated with some examples of molecular recognition/sensing, self-assembly/engineering, receptors, catalysts, supramolecules, graphene, and other two-dimensional (2D) materials/devices.

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“…In fact, they have demonstrated using 1 H NMR titrations that anion-π interactions stabilize the enolate by almost two pK a units. Remarkably, the addition of these anion-π-stabilized reactive enolate intermediates to enones and nitroolefins occurs with significant transition-state stabilizations (up to 11 kJ/mol) [103]. Moreover, anionic cascade reactions that cover aldol condensation, elimination and transesterification also accelerate on π-acidic surfaces.…”

Section: Catalysismentioning

confidence: 97%

“…For instance the more pronounced decrease of the distance between benzisoxazole oxygen and catalyst plane on going from the initial complex to the TS is correlated with the higher strength of the anion-π interaction in the NDI CN . Matile's group has taken one step further the research on anion-π catalysis [103] by extending it to enolate chemistry. They have covalently attached a malonate moiety to an NDI (see Fig.…”

Section: Catalysismentioning

confidence: 99%

Anion-π Interactions in Supramolecular Chemistry and Catalysis

Bauzá

Deyà

Frontera

2015

Challenges and Advances in Computational Chemistry and Physics

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Non-covalent interactions play a major role in supramolecular chemistry and biochemistry by dominating the central parts of living systems since they dictate the functionality of many biological and host-guest systems. A good comprehension of the different non-covalent forces is necessary for the rational design of new drugs and developing improved synthetic receptors capable to function in competitive media. Interactions involving aromatic rings (or π-systems in general) are very relevant in supramolecular chemistry, exemplified by the cation-π interaction and its importance in protein structure and enzyme catalysis. From a traditional point of view, the π-system is usually considered as electron rich (π-basic). The naissance of the counterintuitive anion-π interaction -the attractive interaction between an anion and an electron poor π-system (π-acid)-was somewhat controversially discussed by the scientific community. However, in the last decade a great deal of theoretical and experimental investigations has time-honored the anion-π interaction as an important supramolecular bond. Herein we describe the physical nature of this noncovalent interaction and the different strategies that can be used to modulate its strength. Finally, selected state-of-the-art reports illustrating the rational utilization of the anion-π interaction in supramolecular chemistry (anion receptors), biological applications and catalysis are described in this chapter.

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Enolate chemistry with anion–π interactions

Cited by 74 publications

References 46 publications

Anion‐Binding Catalysis by Electron‐Deficient Pyridinium Cations

Anion‐Binding Catalysis by Electron‐Deficient Pyridinium Cations

Functional molecules and materials by π‐Interaction based quantum theoretical design

Anion-π Interactions in Supramolecular Chemistry and Catalysis

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