Anion–π Catalysis of Diels–Alder Reactions

Liu, Le; Cotelle, Yoann; Bornhof, Anna‐Bea; Besnard, Céline; Sakai, Naomi; Matile, Stefan

doi:10.1002/anie.201707730

Cited by 41 publications

(40 citation statements)

References 41 publications

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“…Supramolecular soft materials 1−6 consisting of organic π-conjugated molecules 7−13 are attracting enormous interest due to their successful applications in organic electronics. The interesting photophysical properties, high π-acidity, and redox behavior of naphthalene diimide (NDI) make it an excellent candidate for various applications.…”

Section: Introductionmentioning

confidence: 99%

Luminescent Naphthalene Diimide-Based Peptide in Aqueous Medium and in Solid State: Rewritable Fluorescent Color Code

et al. 2018

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This study convincingly demonstrates a unique example of the self-assembly of a naphthalene diimide (NDI)-appended peptide into a fluorescent J-aggregate in aqueous media. Moreover, this aggregated species shows a remarkable yellow fluorescence in solid state, an unusual phenomenon for NDI-based compounds. The aggregated species has been characterized using transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy, X-ray diffraction, time-correlated single proton counting (TCSPC), UV–vis, and photoluminescence studies. TEM images reveal cross-linked nanofibrillar morphology of this aggregated species in water (pH 7.4). TCSPC study clearly indicates that the aggregated species in water has a higher average lifetime compared to that of the non-aggregated species. Interestingly, this NDI-based peptide shows H + ion concentration-dependent change in the emission property in water. The fluorescence output is erased completely in the presence of an alkali, and it reappears in the presence of an acid, indicating its erasing and rewritable property. This indicates its probable use in authentication tools for security purposes as a rewritable fluorescence color code. This NDI-appended peptide-based molecule can be used for encryption of information due to erasing and rewritable property of the molecule in the aggregated state in aqueous medium.

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Section: Introductionmentioning

confidence: 99%

Luminescent Naphthalene Diimide-Based Peptide in Aqueous Medium and in Solid State: Rewritable Fluorescent Color Code

et al. 2018

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“…Recently Matile and co‐workers reported an impressive example on use of NDI‐tertiary amine bifunctional system to catalyze Diels‐Alder reaction (Scheme 4). [23] In the anionic [4+2] cycloaddition of 5 H ‐oxazol‐4‐one 13 a and dienophile 14 , excellent exo / endo ‐selectivity and enantioselectivity was obtained with NDIs 12 , but not with the control 17 or Et 3 N. When 5 H ‐thiazol‐4‐one 13 b was subjected, similar selectivity was observed, and an otherwise dominant Michael addition pathway was suppressed. The reaction rate was found to increase with an increase of π acidity.…”

Section: Anion‐π Interaction Engaged In Both Ground and Transition Statesmentioning

confidence: 97%

Putting Anion‐π Interactions at Work for Catalysis

Luo

Wang

et al. 2021

Chemistry A European J

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Since its discovery two decades ago, anion‐π interaction has been increasingly recognized as an important driving force. Extensive theoretical and experimental efforts on the ground‐state anion‐π binding and recognition have laid the bases for exploring its relevance in catalysis. Accordingly, the concept of “anion‐π catalysis” that employing an electron‐deficient π surface (π‐acidic surface) for anionic reaction intermediate and transition state stabilization has emerged. This article shortly reviews the emergence and development of this concept, aiming to provide an emphasis on the general concept and key progress in this exciting area. To highlight the essential contribution of anion‐π interactions, the contents are organized according to their role engaged in catalytic process, for example from both ground‐state and transition‐state stabilization to solely transition‐state stabilization, mainly by a single π‐face, and to cooperative π‐face activation. A concluding remark and outlook on future development of this field is also given.

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“…Moreover, by manipulating asymmetric auxiliaries, contributions from anion‐ π interactions could be expanded from chemoselectivity to stereoselectivity. These have been well exemplified by anion‐ π catalysis in asymmetric enamine and iminium chemistry, transamination, cascade processes and Diels–Alder reactions . Furthermore, biotin‐streptavidin technology provided access to the first anion‐ π enzyme .…”

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 of Diels–Alder Reactions

Cited by 41 publications

References 41 publications

Luminescent Naphthalene Diimide-Based Peptide in Aqueous Medium and in Solid State: Rewritable Fluorescent Color Code

Luminescent Naphthalene Diimide-Based Peptide in Aqueous Medium and in Solid State: Rewritable Fluorescent Color Code

Putting Anion‐π Interactions at Work for Catalysis

Anion‐π Catalysis: Focus on Nonadjacent Stereocenters

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