Copper(I) oxide and benzoic acid ‘on water’: a highly practical and efficient catalytic system for copper(I)-catalyzed azide–alkyne cycloaddition

Shao, Changwei; Zhu, Rui; Luo, Shaobo; Zhang, Qun; Wang, Xinyan

doi:10.1016/j.tetlet.2011.05.061

Cited by 51 publications

(25 citation statements)

References 41 publications

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“…Copper metal is already known as a catalyst source for the CuAAC reaction from reports using copper turnings, 22 copper particles, 23,25,42 and flat copper surfaces 26–28 . In previous reports using a copper surface to initiate CuAAC, generation of the Cu(I) catalyst was attributed to aerobic oxidation of the copper surface, which we presume occurs here.…”

Section: Resultsmentioning

confidence: 99%

Squish and CuAAC: Additive-Free Covalent Monolayers of Discrete Molecules in Seconds

2013

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A terminal alkyne is immobilized rapidly into a full monolayer by squishing a small volume of a solution of the alkyne between an azide-modified surface and a copper plate. The monolayer is covalently attached to the surface through a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction, and the coverages of the immobilized electroactive alkyne species are quantified by cyclic voltammetry. A reaction time of less than twenty seconds is possible with no other reagents required. The procedure is effective in aerobic conditions using either an aqueous or aprotic organic solution of the alkyne (1–100 mM).

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Section: Resultsmentioning

confidence: 99%

Squish and CuAAC: Additive-Free Covalent Monolayers of Discrete Molecules in Seconds

2013

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“…Applying Cu 2 O powder directly in a title reaction usually results an incomplete conversion and also require long reaction time 16 . Efforts have also been made to enhance the catalytic efficiency of Cu 2 O 17 18 19 20 . It is reported that 17 polyvinylpyrrolidone-coated Cu 2 O nanoparticles can act as an efficient catalyst for cycloaddition reactions in water at physiological temperature.…”

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confidence: 99%

Polymer immobilized Cu(I) formation and azide-alkyne cycloaddition: A one potreaction

Islam

Taher

Choudhary

et al. 2015

Sci Rep

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During the polymerization of aniline using copper sulphate, act as an oxidizing agent, the in-situ synthesized Cu(I) ion catalyzed the cyclo-addition between azides and alkynes. This work represents the merging of two steps, synthesis of the catalyst and application of the catalyst, in a one pot reaction. The elimination of the separate catalyst synthesis step is economic in terms of cost and time. As aniline was used as one of the reactant components so there is no requirement to use additional base for this reaction that further eliminates the cost of the process. Again, the catalyst can be readily recovered by filtration and efficiently used for the several sets of reactions without any significant loss of catalytic activity.

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“…However, we observed two interesting phenomena in CuAAC reactions catalyzed by copper(I) carboxylates 20–23 : (a) by using H 2 O as a solvent, CuAAC reactions still gave similarly excellent results; (b) regardless of the purities of copper(I) carboxylates, they all showed similarly excellent catalytic activity. Since copper(I) carboxylates routinely are synthesized from Cu 2 O and the corresponding carboxylic acid anhydrides, these phenomena strongly implied that the premade copper(I) carboxylates may be replaced simply by a combination of Cu 2 O/RCO 2 H. As shown in Scheme , the catalytic activity of the combination of Cu 2 O/HOAc is as high as that of premade copper(I) acetate under the neat conditions.…”

Section: In‐situ Generated 1‐copper(i) Alkynes In Cycloadditionsmentioning

confidence: 99%

In‐situ Generated and Premade 1‐Copper(I) Alkynes in Cycloadditions

Wang

et al. 2017

The Chemical Record

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The copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) was discovered in 2002, which has become the most remarkable example for "click chemistry" to date. In CuAAC reaction, 1-copper(I) alkyne has been recognized to be a key intermediate. However, many contradictory experimental results for this intermediate were reported in literature. For example, only the in-situ generated 1-copper(I) alkyne was used, while the premade 1-copper(I) alkyne proved to be inefficient under the standard conditions. The kinetic studies indicated that CuAAC reaction had a strict second-order dependence on Cu(I) and the DFT studies demonstrated that 1-copper(I) alkyne intermediate should be a dinuclear copper(I) complex. But these results were inconsistent with the structure of the premade 1-copper(I) alkyne. Although hundreds of structurally different ligands were reported to significantly enhance the efficiency of CuAAC reaction, their functions were assigned to prevent the oxidation and the disproportionation of Cu(I) ion. Based on the investigation of the references and our works, we proposed that the in-situ generated 1-copper(I) alkyne in CuAAC reaction is not identical with the premade 1-copper(I) alkyne. The ligands may play dual roles to activate the 1-copper(I) alkyne by blocking the polymerization of the in-situ formed 1-copper(I) alkynes and dissociating the polymeric structures of the premade 1-copper(I) alkynes. As a result, we first disclosed that carboxylic acids can function as such activators and a novel carboxylic acid-catalyzed CuAAC strategy was developed, which has been proven to be the most convenient and highly efficient CuAAC method to date. Furthermore, highly efficient and regioselective methods for the syntheses of 1,4,5-trisubstituted 1,2,3-triazoles were developed by using the premade 1-copper(I) alkynes as substrates, in which the novel function of the premade 1-copper(I) alkynes as excellent dipolarophiles was first disclosed and applied. In this article, a series of works reported by our group for the in-situ generated and the premade 1-copper(I) alkynes in cycloadditions are reviewed.

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Copper(I) oxide and benzoic acid ‘on water’: a highly practical and efficient catalytic system for copper(I)-catalyzed azide–alkyne cycloaddition

Cited by 51 publications

References 41 publications

Squish and CuAAC: Additive-Free Covalent Monolayers of Discrete Molecules in Seconds

Squish and CuAAC: Additive-Free Covalent Monolayers of Discrete Molecules in Seconds

Polymer immobilized Cu(I) formation and azide-alkyne cycloaddition: A one potreaction

In‐situ Generated and Premade 1‐Copper(I) Alkynes in Cycloadditions

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