Anion–π catalysis: bicyclic products with four contiguous stereogenic centers from otherwise elusive diastereospecific domino reactions on π-acidic surfaces

Liu, Le; Cotelle, Yoann; Klehr, Juliane; Sakai, Naomi; Ward, Thomas R.; Matile, Stefan

doi:10.1039/c7sc00525c

Cited by 37 publications

(53 citation statements)

References 35 publications

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“…In these molecular systems( co-crystals, mixed crystals,e tc. [15] NDIsw ith certain substituents, in particularsome core-substituted NDIs, may display fluorescence. [8] However,i ti se xtremely rare to utilize unorthodox anion-p interactions, which have versatile uses in anion/molecule recognition, [9] ion/electron transport, [10] and anion-p catalysis, [11] to construct photoluminescent materials.…”

Section: Introductionmentioning

confidence: 99%

Anion–π Interaction‐Induced Room‐Temperature Phosphorescence of a Polyoxometalate‐Based Charge‐Transfer Hybrid Material

Liao

Meng

Jia

et al. 2018

Chemistry A European J

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Room-temperature phosphorescence (RTP) was realized for the first time in a polyoxometalate-based charge-transfer (CT) hybrid material bearing polyoxometalates (POMs) as electron-donors (D) and rigid naphthalene diimides (NDIs) as electron-acceptors (A), meanwhile, this hybrid material displayed photochromism as well. The significant D-A anion-π interaction induced an additional through-space charge-transfer pathway. The resulting suitable D-A CT states can efficiently bridge the relatively large energy gap between the NDI-localized π-π* and π-π* states and thus trigger the ligand-localized phosphorescence ( π-π*).

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Section: Introductionmentioning

confidence: 99%

Anion–π Interaction‐Induced Room‐Temperature Phosphorescence of a Polyoxometalate‐Based Charge‐Transfer Hybrid Material

Liao

Meng

Jia

et al. 2018

Chemistry A European J

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“…Naturally,t hese anion-p interactions are supported by ion pairing and p-p interactions.However, the latter should be weak in isolated, neutral form and, contrary to anion-p interactions,almost disappear during the cycloaddition. Corroborative support for these conclusions was obtained by the increase in rates with an increase in the p acidity [3] of the NDI in catalysts 3 and 4 compared to 2 (see the Supporting Information, Figure S18). In TS1,t he dienophile is proposed to approach the diene from the side of the p surface to benefit also from dienophile activation by p-p interactions and pre-organizing positioning of the substrates in close proximity,a nd to preserve the anion-p stabilization of the complete system throughout the entire reaction.…”

Section: Angewandte Chemiementioning

confidence: 63%

“…[2] Since then, asymmetric anion-p catalysis has been reported for several reactions, [3] and the first anion-p enzyme [4] and electric-field-assisted anion-p catalysis [5] have been realized. Moving on from coupled cascade cyclizations [3] to concerted cycloadditions,t he Diels-Alder reaction stands out as the grand old classic. [6][7][8][9][10][11][12][13][14][15][16][17] Theu sual mechanism of Diels-Alder reactions involves activation of the dienophile with Lewis acids.…”

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confidence: 99%

“…[15] The endo/exo selectivity of Diels-Alder reactions has further been studied with enzymes,r ibozymes,D NAzymes,c yclodextrins,h emicryptophanes,c apsules,s canning tunneling microscopy break junctions,silica nanopores,chaotropes,and ionic liquids as well as at different voltages or pressures and in different media. [3] All details on catalyst and substrate synthesis can be found in the Supporting Information. [3] All details on catalyst and substrate synthesis can be found in the Supporting Information.…”

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confidence: 99%

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Anion–π Catalysis of Diels–Alder Reactions

et al. 2017

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Among concerted cycloadditions,t he Diels-Alder reaction is the grand old classic,which is usually achieved with acid catalysis.I nt his report, hydroxypyrones,o xa-, and thiazolones are explored because they provide access to anionic dienes.T heir [4+ +2] cycloaddition with cyclic and acyclic dienophiles,such as maleimides and fumarates,affords bicyclic products with four new stereogenic centers.B ifunctional anion-p catalysts composed of amine bases next to the p surface of naphthalenediimides (NDIs) are shown to selectively stabilizet he "open", fully accessible anionic exo transition state on the p-acidic aromatic surface.O ur results also include reactivities that are hard to access with conventional organocatalysts,s uch as the exo-specific and highly enantioselective Diels-Alder reaction of thiazolones and maleimides with complete suppression of the otherwise dominant Michael addition. With increasing p acidity of the anionp catalysts,t he rates,c hemo-, diastereo-, and enantioselectivities increase consistently.

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“…Remote control of heterogeneous anion‐ π catalysis on electrodes by electric fields has been reported as well . However, the asymmetric transformations that have been realized with anion‐ π catalysis so far all generate contiguous stereogenic centers . Moving one step further, the next target was to introduce anion‐ π catalysis to the formation of more demanding nonadjacent stereocenters in acyclic molecules from achiral precursors.…”

Section: Introductionmentioning

confidence: 99%

Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

Zhang

Liu

López‐Andarias

et al. 2018

Helvetica Chimica Acta

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In Memory of Gilbert StorkAnion-p interactions have been recently introduced to catalysis with the idea to stabilize anionic intermediates on p-acidic surfaces. Realized examples include enolate, enamine and iminium chemistry, domino processes and DielsAlder reactions. Moving on from the formation of contiguous stereogenic centers on p-acidic surfaces, herein we report the first asymmetric anion-p catalysis of cascade reactions that afford nonadjacent stereocenters. Conjugate addition-protonation of achiral disubstituted enolate donors to 2-chloroacrylonitrile generates 1,3-nonadjacent stereocenters with moderate enantioselectivity and diastereoselectivity. The explored catalysts operate with complementary naphthalenediimide and fullerene surfaces with highly positive quadrupole moments and high polarizability, respectively, and proximal amine bases. We find that anion-p catalysts can increase the diastereoselectivity of the reaction beyond the maximal 1:4.0 dr with conventional catalysts to maximal 5.3:1 dr on the large fullerene surfaces. The enantioselectivity of anion-p catalysts, best on the confined naphthalenediimide surfaces with strong quadrupole moment, exceed the performance of conventional catalysts except for comparable results with a new, most compact, surprisingly powerful bifunctional control catalyst. Simultaneously increased rates and stereoselectivities compared to control catalysts without p-acidic surface support that contributions of anion-p interactions to the catalytic cascade process are significant.

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Anion–π catalysis: bicyclic products with four contiguous stereogenic centers from otherwise elusive diastereospecific domino reactions on π-acidic surfaces

Abstract: Delocalized over aromatic planes, anion–π interactions emerge as best to stabilize long-distance charge displacements in domino reactions of highest sophistication.

Cited by 37 publications

References 35 publications

Anion–π Interaction‐Induced Room‐Temperature Phosphorescence of a Polyoxometalate‐Based Charge‐Transfer Hybrid Material

Anion–π Interaction‐Induced Room‐Temperature Phosphorescence of a Polyoxometalate‐Based Charge‐Transfer Hybrid Material

Anion–π Catalysis of Diels–Alder Reactions

Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

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