Polyvalent Catalysts Operating on Polyvalent Substrates: A Model for Surface‐Controlled Reactivity

McKay, Craig S.; Finn, M. G.

doi:10.1002/anie.201602797

Cited by 14 publications

(6 citation statements)

References 53 publications

(70 reference statements)

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“…Subsequent work in multiple laboratories has confirmed the superior catalysis of anthranilates over anilines. McKay and Finn described the testing of polyvalent and dendrimer-based anthranilic acid catalysts, confirming superior activity over anilines in dendrimer labeling . Langenhan and co-workers used mono- and bifunctional aniline derivatives for fluorescent conjugation of aldose sugars, and confirmed 5MA as the most effective catalyst among 10 tested …”

Section: Catalysts For Oxime/hydrazone Formationmentioning

confidence: 99%

Oximes and Hydrazones in Bioconjugation: Mechanism and Catalysis

2017

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The formation of oximes and hydrazones is employed in numerous scientific fields as a simple and versatile conjugation strategy. This imine-forming reaction is applied in fields as diverse as polymer chemistry, biomaterials and hydrogels, dynamic combinatorial chemistry, organic synthesis, and chemical biology. Here we outline chemical developments in this field, with special focus on the past ∼10 years of developments. Recent strategies for installing reactive carbonyl groups and α-nucleophiles into biomolecules are described. The basic chemical properties of reactants and products in this reaction are then reviewed, with an eye to understanding the reaction's mechanism and how reactant structure controls rates and equilibria in the process. Recent work that has uncovered structural features and new mechanisms for speeding the reaction, sometimes by orders of magnitude, is discussed. We describe recent studies that have identified especially fast reacting aldehyde/ketone substrates and structural effects that lead to rapid-reacting α-nucleophiles as well. Among the most effective new strategies has been the development of substituents near the reactive aldehyde group that either transfer protons at the transition state or trap the initially formed tetrahedral intermediates. In addition, the recent development of efficient nucleophilic catalysts for the reaction is outlined, improving greatly upon aniline, the classical catalyst for imine formation. A number of uses of such second- and third-generation catalysts in bioconjugation and in cellular applications are highlighted. While formation of hydrazone and oxime has been traditionally regarded as being limited by slow rates, developments in the past 5 years have resulted in completely overturning this limitation; indeed, the reaction is now one of the fastest and most versatile reactions available for conjugations of biomolecules and biomaterials.

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Section: Catalysts For Oxime/hydrazone Formationmentioning

confidence: 99%

Oximes and Hydrazones in Bioconjugation: Mechanism and Catalysis

2017

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“…It would allow for sharper switching between the on and off state and higher rates of catalysis due to increased local concentration. The kinetics of multivalent catalysts and multivalent substrates have been investigated in detail ( 41 , 43 ), and their incorporation in chemical reaction networks could shed more light on analogous molecular mechanisms in biochemical pathways.…”

Section: Discussionmentioning

confidence: 99%

Model-driven engineering of supramolecular buffering by multivalency

Paffen

Teunissen

Greef

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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SignificanceThe ability of chemists to regulate the concentration of molecules is extremely important. However, as reactions are slowly superseded by more complex reaction networks, new ways of regulating molecular concentrations are needed. Recently, we described a system in which the concentration of a monovalent molecule with catalytic activity was buffered over a wide concentration range by its binding to a divalent molecule. Guided by model predictions, we are able to experimentally optimize the system by increasing the valency of the buffer, with even-numbered valencies displaying superior buffering capabilities. These results allow us to understand and gain more control over the activities of molecules in complex molecular systems, thereby obtaining insights into natural systems as well as creating adaptive artificial systems.

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“…Further, it was continued by the corporate world in 1980 with the dendritic polylysine by Denkewalter (Allied Corporation) and poly(amidoamine)dendrimers (PAMAM) by Tomalia (Dow Chemical). Dendrimers have seen a wide range of applications in various fields, such as protein mimetics, light-harvesting devices, nanomedicine, drug delivery system, sensors, and effective catalytic systems . A typical dendrimer can be built upon an initiator core, several interior branching layers with multiple connections, and end groups.…”

Section: Cuaac Click Chemistry Mediated Synthesis Of Diverse Glycocon...mentioning

confidence: 99%

Cu(I)-Catalyzed Click Chemistry in Glycoscience and Their Diverse Applications

et al. 2021

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Copper(I)-catalyzed 1,3-dipolar cycloaddition between organic azides and terminal alkynes, commonly known as CuAAC or click chemistry, has been identified as one of the most successful, versatile, reliable, and modular strategies for the rapid and regioselective construction of 1,4-disubstituted 1,2,3-triazoles as diversely functionalized molecules. Carbohydrates, an integral part of living cells, have several fascinating features, including their structural diversity, biocompatibility, bioavailability, hydrophilicity, and superior ADME properties with minimal toxicity, which support increased demand to explore them as versatile scaffolds for easy access to diverse glycohybrids and well-defined glycoconjugates for complete chemical, biochemical, and pharmacological investigations. This review highlights the successful development of CuAAC or click chemistry in emerging areas of glycoscience, including the synthesis of triazole appended carbohydrate-containing molecular architectures (mainly glycohybrids, glycoconjugates, glycopolymers, glycopeptides, glycoproteins, glycolipids, glycoclusters, and glycodendrimers through regioselective triazole forming modular and bio-orthogonal coupling protocols). It discusses the widespread applications of these glycoproducts as enzyme inhibitors in drug discovery and development, sensing, gelation, chelation, glycosylation, and catalysis. This review also covers the impact of click chemistry and provides future perspectives on its role in various emerging disciplines of science and technology.

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Polyvalent Catalysts Operating on Polyvalent Substrates: A Model for Surface‐Controlled Reactivity

Cited by 14 publications

References 53 publications

Oximes and Hydrazones in Bioconjugation: Mechanism and Catalysis

Oximes and Hydrazones in Bioconjugation: Mechanism and Catalysis

Model-driven engineering of supramolecular buffering by multivalency

Cu(I)-Catalyzed Click Chemistry in Glycoscience and Their Diverse Applications

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