Isolation of an acetylide-CuI3-tris(triazolylmethyl)amine complex active in the CuAAC reaction

Chen, Haoqing; Soubra‐Ghaoui, Chirine; Zhu, Zhiling; Albright, Thomas A.; Cai, Chengzhi

doi:10.1016/j.jcat.2018.02.024

Cited by 9 publications

(4 citation statements)

References 68 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Further studies were focused on compounds 9 and 10 , since they exhibited superior gelation properties compared to the rest. The possible ligand and copper ion interactions are shown in the scheme, based on several reports in the literature on the mechanisms of tris(triazolyl methyl)-amine-type ligands [ 44 , 45 , 46 , 47 ].…”

Section: Resultsmentioning

confidence: 99%

Synthesis of a Series of Trimeric Branched Glycoconjugates and Their Applications for Supramolecular Gels and Catalysis

et al. 2023

View full text Add to dashboard Cite

Carbohydrate-derived molecular gelators have found many practical applications as soft materials. To better understand the structure and molecular gelation relationship and further explore the applications of sugar-based gelators, we designed and synthesized eight trimeric branched sugar triazole derivatives and studied their self-assembling properties. These included glucose, glucosamine, galactose, and maltose derivatives. Interestingly, the gelation properties of these compounds exhibited correlations with the peripheral sugar structures. The maltose derivative did not form gels in the tested solvents, but all other compounds exhibited gelation properties in at least one of the solvents. Glucose derivatives showed superior performance, followed by glucosamine derivatives. They typically formed gels in toluene and alcohols; some formed gels in ethanol-water mixtures or DMSO water mixtures. The glycoclusters 9 and 10 demonstrated rate acceleration for the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions. These were further studied for their metallogels formation properties, and the copper metallogels from compound 9 were successfully utilized to catalyze click reactions. These metallogels were able to form a gel column, which was effective in converting the reactants into the triazole products in multiple cycles. Moreover, the same gel column was used to transform a second click reaction using different reactants. The synthesis and characterization of these compounds and their applications for catalytic reactions were discussed.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis of a Series of Trimeric Branched Glycoconjugates and Their Applications for Supramolecular Gels and Catalysis

et al. 2023

View full text Add to dashboard Cite

show abstract

“…Because of the flexibility of the system, the exact geometries of the active species can vary depending on the ligands and the reaction conditions, but the general steps remain the same. − ,,,− The rate-determining step (RDS) depends also on the reaction conditions . In aprotic conditions, the proton transfer from the alkyne to the triazolyl complex happens in one concerted step and is the RDS.…”

Section: Introductionmentioning

confidence: 95%

Concerted Cycloaddition Mechanism in the CuAAC Reaction Catalyzed by 1,8-Naphthyridine Dicopper Complexes

Héron

Balcells

2022

ACS Catal.

View full text Add to dashboard Cite

Copper-catalyzed azide-alkyne cycloaddition (CuAAC) is one of the most versatile reactions in the "click chemistry" toolbox, and its development has made the synthesis of 1,4-triazole derivatives robust and efficient. In this work, we present a density functional theory (DFT) study on the mechanism of the CuAAC reaction catalyzed by a dicopper complex supported by a nonsymmetric 1,8-naphtyridine ligand bearing two different metalcoordinating substituents (i.e., −P(tBu) 2 and −C(Me)(Py) 2 ). The calculations showed that the cycloaddition of the azide to the alkyne occurs in a single concerted step, in contrast with the two-step mechanism proposed in the literature. The energies predicted for this step indicated that the 1,4-triazole isomer of the product is formed in a selective manner, in agreement with experiments. Further, the DFT results showed that there is a subtle and complex interplay between several variables, including the relative orientation of the two substrates, the position of the counter-anion, and the partial decoordination of the 1,8-naphtyridine ligand. A series of 90 transition state calculations showed that, on average, the impact of these variables is strong on the structures but soft on the energy barriers, highlighting the flexible nature of the bonding within the coordination sphere of the bimetallic core of the catalyst. The insight provided by this study will be valuable for the further development of dicopper catalysts for the CuAAC reaction.

show abstract

“…DFT calculations show a decrease in the activation barrier when a second Cu atom is introduced . In addition, various isolable polynuclear copper acetylide complexes were found to be catalytically active in the CuAAC reaction. − Based on these observations, catalysis is believed to proceed through dinuclear Cu I intermediates (Scheme c).…”

Section: Introductionmentioning

confidence: 99%

Cationic Copper Iminophosphorane Complexes as CuAAC Catalysts: A Mechanistic Study

et al. 2020

View full text Add to dashboard Cite

We have combined Cu K-edge X-ray absorption spectroscopy with NMR spectroscopy ( 1 H and 31 P) to study the Cu-catalyzed azide−alkyne cycloaddition (CuAAC) reaction under operando conditions. A variety of novel, well-defined Cu I iminophosphorane complexes were prepared. These ligands, based on the in situ Staudinger reduction when [Cu(PPh 3 ) 3 Br] is employed, were found to be active catalysts in the CuAAC reaction. Here, we highlight recent advances in mechanistic understanding of the CuAAC reaction using spectroscopic and kinetic investigations under strict air-free and operando conditions. A mononuclear Cu triazolide intermediate is identified to be the resting state during catalysis; cyclization and protonation both have an effect on the rate of the reaction. A key finding of this study includes a novel group of highly modular Cu I complexes that are active in the base-free CuAAC reaction.

show abstract

Isolation of an acetylide-CuI3-tris(triazolylmethyl)amine complex active in the CuAAC reaction

Cited by 9 publications

References 68 publications

Synthesis of a Series of Trimeric Branched Glycoconjugates and Their Applications for Supramolecular Gels and Catalysis

Synthesis of a Series of Trimeric Branched Glycoconjugates and Their Applications for Supramolecular Gels and Catalysis

Concerted Cycloaddition Mechanism in the CuAAC Reaction Catalyzed by 1,8-Naphthyridine Dicopper Complexes

Cationic Copper Iminophosphorane Complexes as CuAAC Catalysts: A Mechanistic Study

Contact Info

Product

Resources

About