Enantioselective Cu<sup>II</sup>‐Catalyzed Diels–Alder and Michael Addition Reactions in Water Using Bio‐Inspired Triazacyclophane‐Based Ligands

Albada, Bauke; Rosati, Fiora; Coquière, David; Roelfes, Gérard; Liskamp, Rob M. J.

doi:10.1002/ejoc.201001522

Cited by 16 publications

(3 citation statements)

References 45 publications

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“…To account for the different catalytic activities of nucleoapzymes in configurations I, II, and III, we have implemented molecular dynamics simulations using the YASARA Structure software package. , Previous studies have successfully applied this software for the computational analysis of aptamer-ligand complexes . Accordingly, we have applied the method to generate a plausible structural model for the aptamer-dopamine complex (for details, see Experimental Section and Supporting Information).…”

Section: Results and Discussionmentioning

confidence: 99%

Nucleoapzymes: Hemin/G-Quadruplex DNAzyme–Aptamer Binding Site Conjugates with Superior Enzyme-like Catalytic Functions

et al. 2015

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A novel concept to improve the catalytic functions of nucleic acids (DNAzymes) is introduced. The method involves the conjugation of a DNA recognition sequence (aptamer) to the catalytic DNAzyme, yielding a hybrid structure termed "nucleoapzyme". Concentrating the substrate within the "nucleoapzyme" leads to enhanced catalytic activity, displaying saturation kinetics. Different conjugation modes of the aptamer/DNAzyme units and the availability of different aptamer sequences for a substrate provide diverse means to design improved catalysts. This is exemplified with (i) The H2O2-mediated oxidation of dopamine to aminochrome using a series of hemin/G-quadruplex-dopamine aptamer nucleoapzymes. All nucleoapzymes reveal enhanced catalytic activities as compared to the separated DNAzyme/aptamer units, and the most active nucleoapzyme reveals a 20-fold enhanced activity. Molecular dynamics simulations provide rational assessment of the activity of the various nucleoapzymes. The hemin/G-quadruplex-aptamer nucleoapzyme also stimulates the chiroselective oxidation of L- vs D-DOPA by H2O2. (ii) The H2O2-mediated oxidation of N-hydroxy-L-arginine to L-citrulline by a series of hemin/G-quadruplex-arginine aptamer conjugated nucleoapzymes.

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Section: Results and Discussionmentioning

confidence: 99%

Nucleoapzymes: Hemin/G-Quadruplex DNAzyme–Aptamer Binding Site Conjugates with Superior Enzyme-like Catalytic Functions

et al. 2015

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“…Liskamp and co-workers developed a triazacyclophane (TAC) scaffold with three histidine amino acid residues as a tridentate ligand for copper(II)-catalyzed Diels−Alder reactions (Scheme 43). 107 The enantioselectivity was very sensitive to the structure of the macrocycles. Extensions at the N-termini of the histidine residues other than the acetyl group, or the insertion of amino acid residues between the histidine residues and the TAC scaffold, resulted in a significant drop in enantioselectivity.…”

Section: Metal-based Catalystsmentioning

confidence: 99%

Catalytic Organic Reactions in Water toward Sustainable Society

et al. 2017

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Traditional organic synthesis relies heavily on organic solvents for a multitude of tasks, including dissolving the components and facilitating chemical reactions, because many reagents and reactive species are incompatible or immiscible with water. Given that they are used in vast quantities as compared to reactants, solvents have been the focus of environmental concerns. Along with reducing the environmental impact of organic synthesis, the use of water as a reaction medium also benefits chemical processes by simplifying operations, allowing mild reaction conditions, and sometimes delivering unforeseen reactivities and selectivities. After the "watershed" in organic synthesis revealed the importance of water, the development of water-compatible catalysts has flourished, triggering a quantum leap in water-centered organic synthesis. Given that organic compounds are typically practically insoluble in water, simple extractive workup can readily separate a water-soluble homogeneous catalyst as an aqueous solution from a product that is soluble in organic solvents. In contrast, the use of heterogeneous catalysts facilitates catalyst recycling by allowing simple centrifugation and filtration methods to be used. This Review addresses advances over the past decade in catalytic reactions using water as a reaction medium.

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“…Pioneering works in this field were published in 2011 by Roelfes, Liskamp, and co-workers, with the 1,4-addition of dimethyl malonate to cinnamyl 2-acyl-1-methylimidazole (31). Unfortunately, in the presence of Cu(NO 3 ) 2 and the triazacyclo- phane-based ligand L12, the product was obtained in a good yield of 90%, but a poor enantioselectivity (24% ee) was observed (Scheme 14) [35].…”

Section: αβ-Unsaturated Acylimidazolesmentioning

confidence: 99%

Copper-catalyzed enantioselective conjugate addition of organometallic reagents to challenging Michael acceptors

Pichon¹,

Morvan²,

Crévisy³

et al. 2020

Beilstein J. Org. Chem.

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The copper-catalyzed enantioselective conjugate addition (ECA) of organometallic nucleophiles to electron-deficient alkenes (Michael acceptors) represents an efficient and attractive methodology for providing a wide range of relevant chiral molecules. In order to increase the attractiveness of this useful catalytic transformation, some Michael acceptors bearing challenging electron-deficient functions (i.e., aldehydes, thioesters, acylimidazoles, N-acyloxazolidinones, N-acylpyrrolidinones, amides, N-acylpyrroles) were recently investigated. Remarkably, only a few chiral copper-based catalytic systems have successfully achieved the conjugate addition of different organometallic reagents to these challenging Michael acceptors, with excellent regio- and enantioselectivity. Furthermore, thanks to their easy derivatization, the resulting chiral conjugated products could be converted into various natural products. The aim of this tutorial review is to summarize recent advances accomplished in this stimulating field.

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Enantioselective Cu^II‐Catalyzed Diels–Alder and Michael Addition Reactions in Water Using Bio‐Inspired Triazacyclophane‐Based Ligands

Cited by 16 publications

References 45 publications

Nucleoapzymes: Hemin/G-Quadruplex DNAzyme–Aptamer Binding Site Conjugates with Superior Enzyme-like Catalytic Functions

Nucleoapzymes: Hemin/G-Quadruplex DNAzyme–Aptamer Binding Site Conjugates with Superior Enzyme-like Catalytic Functions

Catalytic Organic Reactions in Water toward Sustainable Society

Copper-catalyzed enantioselective conjugate addition of organometallic reagents to challenging Michael acceptors

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Enantioselective CuII‐Catalyzed Diels–Alder and Michael Addition Reactions in Water Using Bio‐Inspired Triazacyclophane‐Based Ligands

Cited by 16 publications

References 45 publications

Nucleoapzymes: Hemin/G-Quadruplex DNAzyme–Aptamer Binding Site Conjugates with Superior Enzyme-like Catalytic Functions

Nucleoapzymes: Hemin/G-Quadruplex DNAzyme–Aptamer Binding Site Conjugates with Superior Enzyme-like Catalytic Functions

Catalytic Organic Reactions in Water toward Sustainable Society

Copper-catalyzed enantioselective conjugate addition of organometallic reagents to challenging Michael acceptors

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Product

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Enantioselective Cu^II‐Catalyzed Diels–Alder and Michael Addition Reactions in Water Using Bio‐Inspired Triazacyclophane‐Based Ligands