“Click” Chemistry in a Supramolecular Environment: Stabilization of Organogels by Copper(I)-Catalyzed Azide−Alkyne [3 + 2] Cycloaddition (original) (raw)
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Copper(II)-dipicolinate-mediated clickable azide–alkyne cycloaddition in water as solvent
Journal of Coordination Chemistry
Copper(II)-dipicolinate complex [Cu II L(H 2 O) 2 ] (1), (H 2 L = dipicolinic acid (H 2 dipic)) was synthesized via oxidation reaction of copper(I) iodide and pyridine-2,6-dicarboxylic acid in water and acetonitrile in presence of glycine. Complex 1 was characterized by FT-IR and elemental analysis and its structure confirmed by single crystal X-ray analysis. This complex is an efficient precatalyst that mediates azide-alkyne cycloaddition reactions in water at room temperature either in the absence or presence of a reducing agent. Compound 1-mediated azide-alkyne cycloaddition affords alkyl/aryl substituted 1,2,3-triazole heterocycles in a regioselective manner and excellent yields under very mild reaction conditions matching the criteria of greener protocols.
The Journal of Organic Chemistry, 2013
An efficient method for attachment of a variety of reporter groups to oligonucleotides (ONs) is copper (I) [Cu(I)]-catalyzed Huisgen azide-alkyne 1,3dipolar cycloaddition ("click reaction"). However, in the case of ONs with phosphorothioate modifications as internucleosidic linkages (PS-ONs), this conjugation method has to be adjusted to be compatible with the sulfurcontaining groups. The method described here is adapted for PS-ONs, utilizes solid-supported ONs, and implements the Cu(I) bromide dimethyl sulfide complex (CuBr × Me 2 S) as a mediator for the click reaction. The solid-supported ONs can be readily transformed into "clickable ONs" by on-line addition of an alkyne-containing linker that subsequently can react with an azido-containing moiety (e.g., a peptide) in the presence of CuBr × Me 2 S.
Arkivoc
A typical 1,2,3-triazoles are important aromatic heterocyclic compounds with three adjacent nitrogen atoms. These "unnatural" heterocycles found applications in pharmaceutical science, material science and chemical biology. Oligo-1,2,3-triazole linked molecules showed interesting applications in the field of DNA binding, selfassembly, surface modification, supramolecular chemistry etc. In this article, oligo-1,2,3-triazoles are broadly classified into two categories: (i) 1,2,3-triazoles are connected through varieties of organic molecules and (ii) triazole units are connected with one another either by N-(CH)n-C linkages or by amide bonds generated from amino acids. Syntheses and properties of some of these oligomers are reviewed in this article.
Beyond copper-catalyzed azide-alkyne 1,3-dipolar cycloaddition: Synthesis and mechanism insights
Tetrahedron, 2019
The first proposed mechanism for a CuAAC reaction was described by Sharpless and Fokin (Scheme 2). 2 The formation of copper(I) acetylide is initially observed and then the azide is activated by coordination to the metal center producing an intermediate between the two species, that is, the azide and the acetylene. The following step is the C-N bond-forming which proceeds via a strained six-membered copper-containing intermediate. A reductive elimination is finally accomplished with the second C-N bond-forming leading to the formation of the 1,4-regioisomer of the 1,2,3-triazole adduct (Scheme 2). Scheme 1. Example of a Huisgen 1,3-dipolar cycloaddition and copper-catalyzed azidealkyne cycloaddition (CuAAC).
Star polymers by photoinduced copper-catalyzed azide-alkyne cycloaddition click chemistry
Journal of Polymer Science Part A: Polymer Chemistry, 2015
Well-defined star polymers consisting of tri-, tetra-, or octa-arms have been prepared via coupling-onto strategy using photoinduced copper(I)-catalyzed 1,3-dipolar cycloaddition click reaction. An azide end-functionalized polystyrene and poly(methyl methacrylate), and an alkyne end-functionalized poly(e-caprolactone) as the integrating arms of the star polymers are prepared by the combination of controlled polymerization and nucleophilic substitution reactions; whereas, multifunctional cores containing either azide or alkyne functionalities were synthesized in quantitatively via etherification and ring-opening reactions. By using photoinduced coppercatalyzed azide-alkyne cycloaddition (CuAAC) click reaction, reactive linear polymers are simply attached onto multifunctional cores to form corresponding star polymers via couplingonto methodology. The chromatographic, spectroscopic, and thermal analyses have clearly demonstrated that successful star formations can be obtained via photoinduced CuAAC click reaction. V
Solvent-Free Copper-Catalyzed Azide-Alkyne Cycloaddition under Mechanochemical Activation
Molecules (Basel, Switzerland), 2015
The ball-mill-based mechanochemical activation of metallic copper powder facilitates solvent-free alkyne-azide click reactions (CuAAC). All parameters that affect reaction rate (i.e., milling time, revolutions/min, size and milling ball number) have been optimized. This new, efficient, facile and eco-friendly procedure has been tested on a number of different substrates and in all cases afforded the corresponding 1,4-disubstituted 1,2,3-triazole derivatives in high yields and purities. The final compounds were isolated in almost quantitative overall yields after simple filtration, making this procedure facile and rapid. The optimized CuAAC protocol was efficiently applied even with bulky functionalized β-cyclodextrins (β-CD) and scaled-up to 10 g of isolated product.