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• 31106-82-8 2-(bromomethyl)pyridine hydrobromide 
• 2101-87-3 p-methoxy-phenylazide 

Relevant academic research and scientific papers

Synthesis and NMR analysis of 1,4-disubstituted 1,2,3-triazoles tethered to pyridine, pyrimidine, and pyrazine rings

A combinatorial modular approach based on the "click" copper(I)-catalysed azide-alkyne cycloaddition reaction was used to prepare a library of selected 1,4-disubstituted 1,2,3-triazoles differently functionalized with heteroaryl groups including pyridine,

A Bioorthogonal Small Molecule Selective Polymeric "clickase"

Synthetic polymer scaffolds may serve as gatekeepers preventing the adhesion of biomacromolecules. Herein, we use gating to develop a copper-containing single-chain nanoparticle (SCNP) catalyst as an artificial "clickase"that operates selectively on small

Arylation of Click Triazoles with Diaryliodonium Salts

A robust, selective, and highly efficient method for the preparation of 1,3,4-triaryl 1,2,3-triazolium salts has been developed. It features arylation of a click triazole with a diaryliodonium salt in the presence of a copper catalyst under neat condition

Heterothiometallic clusters as robust and efficient copper(I) catalysts for azide-alkyne [3 + 2] cycloadditions

We investigated heterothiometallic W(Mo)/S/Cu clusters [NH4]2[MS4CunXn] (M = W, Mo; X = Br, I; n = 2, 4, 6) as novel copper(I) catalysts for Huisgen 1,3-dipolar cycloadditions. The experiments indicat

Luminescent Iridium(III) Cyclometalated Complexes with 1,2,3-Triazole "Click" Ligands

A series of cyclometalated iridium(III) complexes with either 4-(2-pyridyl)-1,2,3-triazole or 1-(2-picolyl)-1,2,3-triazole ancillary ligands to give complexes with either 5- or 6-membered chelate rings were synthesized and characterized by a combination of X-ray crystallography, electron spin ionization-high-resolution mass spectroscopy (ESI-HRMS), and nuclear magnetic resonance (NMR) spectroscopy. The electronic properties of the complexes were probed using absorption and emission spectroscopy, as well as cyclic voltammetry. The relative stability of the complexes formed from each ligand class was measured, and their excited-state properties were compared. The emissive properties are, with the exception of complexes that contain a nitroaromatic substituent, insensitive to functionalization of the ancillary pyridyl-1,2,3-triazole ligand but tuning of the emission maxima was possible by modification of the cyclometalating ligands. It is possible to prepare a wide range of optimally substituted pyridyl-1,2,3-triazoles using copper Cu(I)-catalyzed azide alkyne cycloaddition, which is a commonly used "click" reaction, and this family of ligands represent an useful alternative to bipyridine ligands for the preparation of luminescent iridium(III) complexes.

Mechanism of Copper(I)-Catalyzed 5-Iodo-1,2,3-triazole Formation from Azide and Terminal Alkyne

5-Iodo-1,2,3-triazole (iodotriazole) can be prepared from a copper(I)-catalyzed reaction between azide and terminal alkyne in the presence of an iodinating agent, with 5-protio-1,2,3-triazole (protiotriazole) as the side product. The increasing utilities of iodotriazoles in synthetic and supramolecular chemistry drive the efforts in improving their selective syntheses based on a sound mechanistic understanding. A routinely proposed mechanism takes the cue from the copper(I)-catalyzed azide-alkyne cycloaddition, which includes copper(I) acetylide and triazolide as the early and the late intermediates, respectively. Instead of being protonated to afford protiotriazole, an iodinating agent presumably intercepts the copper(I) triazolide to give iodotriazole. The current work shows that copper(I) triazolide can be iodinated to afford iodotriazoles. However, when the reaction starts from a terminal alkyne as under the practical circumstances, 1-iodoalkyne (iodoalkyne) is an intermediate while copper(I) triazolide is bypassed on the reaction coordinate. The production of protiotriazole commences after almost all of the iodoalkyne is consumed. Using 1H NMR to follow a homogeneous iodotriazole forming reaction, the rapid formation of an iodoalkyne is shown to dictate the selectivity of an iodotriazole over a protiotriazole. To ensure the exclusive production of iodotriazole, the complete conversion of an alkyne to an iodoalkyne has to, and can be, achieved at the early stage of the reaction.

Fac- Re(CO)3Cl complexes of [2-(4-R-1 H -1,2,3-Triazol-1-yl) methyl]pyridine inverse click ligands: A systematic synthetic, spectroscopic, and computational study

A series of electronically tuned fac-Re(CO)3Cl inverse pyridyl-1,2,3-triazole complexes have been synthesized in good to excellent yields (72-95%) by refluxing methanol solutions of [Re(CO)5Cl] and the substituted [2-(4-R-1H-1,2,3-triazol-1-yl)methyl]pyridine ligands (py(CH2)tri-R). The resulting rhenium(I) complexes were characterized by elemental analysis, HR-ESI-MS and IR and 1H and 13C NMR spectroscopy. Additionally, the molecular structures of three of the complexes were confirmed using X-ray crystallography. The electronic properties of this series of fac-[(py(CH2)tri-R)Re(CO)3Cl] complexes were examined using UV-vis, Raman, and emission spectroscopy and cyclic voltammetry techniques. The complexes exhibit intense absorptions in the UV region, which were modeled using time-dependent density functional theory (TD-DFT). The calculations suggest that the lower energy part of the absorption band is MLCT in nature and additional higher energy π-π* transitions are present. The electronic spectra are nearly identical for all except where R = 4-nitrophenyl, suggesting that the 1,2,3-triazolyl unit acts as an electronic insulator. The TD-DFT calculations suggest that the lowest energy MLCT transition is polarized to the pyridine moiety for all complexes except the nitro-substituted one. With R = 4-nitrophenyl the MLCT is directed to an acceptor MO polarized to the triazole-R moiety. This finding is supported by resonance Raman studies that show enhancement of modes associated with the triazole-R group. The complexes are weakly emissive at room temperature with quantum yields -3 and correspondingly short excited-state lifetimes (τ 20 ns). The electrochemistry of the complexes is defined by quasi-reversible Re oxidation and irreversible triazole-based ligand reduction processes. The nitro-substituted complexes show additional nitrobenzene-type reduction features. Consistent with the spectroscopic data, the positions of the oxidation and reduction processes are essentially unaffected by the electronic nature of the 2-(4-R-1H-1,2,3-triazol-1-yl)pyridine substituent.

Chelation-assisted, copper(II)-acetate-accelerated azide-alkyne cycloaddition

We described in a previous communication a variant of the popular Cu I-catalyzed azide-alkyne cycloaddition (AAC) process where 5 mol % of Cu(OAc)2 in the absence of any added reducing agent is sufficient to enable the reaction. 2-Picolylazide (1) and 2-azidomethylquinoline (2) were found to be by far the most reactive carbon azide substrates that convert to 1,2,3-triazoles in as short as a few minutes under the discovered conditions. We hypothesized that the abilities of 1 and 2 to chelate CuII contribute significantly to the observed high reaction rates. The current work examines the effect of auxiliary ligands near the azido group other than pyridyl for CuII on the efficiency of the Cu(OAc)2-accelerated AAC reaction. The carbon azides capable of binding to the catalytic copper center at the alkylated azido nitrogen in a chelatable fashion were indeed shown to be superior substrates under the reported conditions. The chelation between carbon azide 11 and CuII was demonstrated in an X-ray single-crystal structure. In a limited set of examples, the ligand tris(benzyltriazolylmethyl) amine (TBTA), developed by Fokin et al. for assisting the original Cu I-catalyzed AAC reactions, also dramatically enhances the Cu(OAc)2-accelerated AAC reactions involving nonchelating azides. This observation leads to the hypothesis of an additional effect of chelating azides on the efficiencies of Cu(OAc)2-accelerated AAC reactions, which is to facilitate the rapid reduction of CuII to highly catalytic CuI species. Mechanistic studies on the AAC reactions with particular emphasis on the role of carbon azide/copper interactions will be conducted based on the observations reported in this work. Finally, the immediate utility of the product 1,2,3-triazole molecules derived from chelating azides as multidentate metal coordination ligands is demonstrated. The resulting triazolyl-containing ligands are expected to bind with transition metal ions via the N(2) nitrogen of the 1,2,3-triazolyl group to form nonplanar coordination rings. The CuII complexes of bidentate T1 and tetradentate T6 and the ZnII complex of T6 were characterized by X-ray crystallography. The structure of [Cu(T1)2(H2O) 2](ClO4)2 reveals the interesting synergistic effect of hydrogen bonding, π-π stacking interactions, and metal coordination in forming a one-dimensional supramolecular construct in the solid state. The tetradentate coordination mode of T6 may be incorporated into designs of new molecule sensors and organometallic catalysts.