Regioselective [3+4] cycloaddition of an azomethine ylide to meso-meso, β-β, β′-β′ triply linked diporphyrins

Thermal reaction of meso-meso, β-β, β′-β′ triply linked diporphyrins with an azomethine ylide produced seven-membered cycloadducts via formal [3+4] cycloaddition at the bay-area. Bischlorin structures of the cycloadducts are characterized on the basis of spectroscopic data and confirmed by single crystal X-ray diffraction analysis. Interestingly, the stability of the cycloadducts depends on the central metal ions in the porphyrin core.     

Metal ion detection using a fluorogenic ‘click’ reaction

A fluorogenic Cu(I)-catalyzed azide-alkyne cycloaddition reaction (CuAAC) of 3-azido-7-hydroxycoumarin has been used to detect metal ions in solution. The formation of a highly fluorescent triazole product signals the presence of Cu(I) or Cu(II) ions at micromolar concentrations. CuAAC can be modified by using an exogenous ligand like EDTA to detect and quantify Zn(II), Ca(II), and Cd(II) ions at micromolar concentrations by an allosteric mechanism. The increase in the formation of the triazole product is regulated by the release of Cu(II) from the Cu(II)-EDTA complex by the addition of a second metal ion, the allosteric effector.     

Rhodamine triazole-based fluorescent probe for the detection of Pt(2+)

A rhodamine triazole-based fluorescent chemosensor has been developed for the selective detection of platinum ions in aqueous solutions. The rhodamine 6G hydroxamate linked with a propargyl group is converted to the corresponding triazole by a "click" reaction. The dual binding unit composed of a hydroxamate and a triazole shows high selectivity and sensitivity toward Pt(2+) over a range of other metal ions in water. The fluorescent probe is applied to monitor cisplatin in aqueous solutions.     

Cyclointercalands.- Incorporation of the phenazine group and of metal binding subunits into macrocyclic receptor molecules.

Macrocyclic receptor molecules containing two phenazine groups 1, or combining a phenazine unit and a metal ion binding site, 2 and 3, have been synthesized; evidence has been obtained for the binding of anionic substrate to the bis-N-methylated 1-Me₂²+ and of metal ions (Ag+, Cu+) to 2 and 3.     

Porous,Conductive Metal‐Triazolates and Their Structural Elucidation by the Charge‐Flipping Method

A new family of porous crystals was prepared by combining 1H‐1,2,3‐triazole and divalent metal ions (Mg, Mn, Fe, Co, Cu, and Zn) to give six isostructural metal‐triazolates (termed MET‐1 to 6). These materials are prepared as microcrystalline powders, which give intense X‐ray diffraction lines. Without previous knowledge of the expected structure, it was possible to apply the newly developed charge‐flipping method to solve the complex crystal structure of METs: all the metal ions are octahedrally coordinated to the nitrogen atoms of triazolate such that five metal centers are joined through bridging triazolate ions to form super‐tetrahedral units that lie at the vertexes of a diamond‐type structure. The variation in the size of metal ions across the series provides for precise control of pore apertures to a fraction of an Angstrom in the range 4.5 to 6.1 Å. MET frameworks have permanent porosity and display surface areas as high as some of the most porous zeolites, with one member of this family, MET‐3, exhibiting significant electrical conductivity.     

Azo dyes from 2-amino-1,3,4-thiodiazole

Thiodiazolyazo dyes from resorcinol, p-cresol and beta-naphthol have been prepared. They are inferior to their thiazole and triazole analogues in their colour-forming reactions with metal ions.     

Isocyanate-, isothiocyanate-, urea-, and thiourea-substituted boron dipyrromethene dyes as fluorescent probes

Boron dipyrromethene dyes (Bodipy) bearing a meso-phenyl substituent carrying a variety of functional groups can be prepared under mild conditions. A single-crystal X-ray structure determination for the 3,5-dinitrophenyl compound shows the phenyl ring to be almost orthogonal (dihedral angle 84 degrees) to the plane of the Bodipy core, with one nitro group almost coplanar with the ring and the other tilted by approximately 21 degrees. Nitro substituents at the 3-, 4-, and 5- positions of the phenyl group are readily reduced to the corresponding amino groups and then converted to isocyanato, isothiocyanato, urea, thiourea, and some polyimine derivatives, the last providing additional functionality (phenazine and pyridylindole units) suitable for chelation of metal ions. All compounds are redox active, the electron-transfer processes being assigned on the basis of comparisons with model compounds. Their fluorescence properties are sensitive to the phenyl group substituents. The Bodipy unit excited state appears to be a strong reductant (Eo approximately -1.4 V) and a modest oxidant (Eo approximately +1.0 V). Quenching processes in the nitro and phenazine derivatives appear to involve intramolecular photoinduced electron transfer.     

Synthesis of modified triazole nucleosides possessing one or two base moieties via a click chemistry approach

Copper-catalyzed 1,3-dipolar cycloaddition of propargyl and azidoethyl thymine and adenine derivatives afforded triazole nucleosides bearing one or two base moieties. A catalytic role of the adenine nucleus was observed and is explained through copper-adenine coordination in the intermediate copper acetylide-azide complex. The antioxidant activity of the obtained cycloadducts was tested.     

Coordination‐driven self‐assembly of Cp*Rh‐based rectangles in novel families of hetero‐bimetallic metal–organic frameworks

The crystal and molecular structures of a series of structurally related 1,2,3‐triazole‐4,5‐dicarboxylate (LHtzdc = 1,2,3‐triazole‐4,5‐dicarboxylate) ligands for second metal ions were established via single‐crystal X‐ray structural analysis. [Cu (en)]²⁺ (en = ethylenediamine) was selected as a second metal ion, the two spare sites of the O atom from LHtzdc are coordinated to a single [Cu (en)]²⁺, and the [Cu (en)]²⁺ metal centres act as two outer pockets, which is an effective and innovative method of controlling the assembly of heterometallic cages.     

Click To Bind: Metal Sensors

The copper‐catalyzed azide–alkyne “click” cycloaddition reaction is an efficient coupling reaction that results in the formation of a triazole ring. The wide range of applicable substrates for this reaction allows the construction of a variety of conjugated systems. The additional function of triazoles as metal‐ion ligands has led to the click reaction being used for the construction of optical sensors for metal ions. The triazoles are integral binding elements, which are formed in an efficient modular synthesis. Herein, we review recent examples of triazoles as a metal‐binding element in conjugated metal‐ion sensors.     

Click chemistry with O-dimethylpropargylcarbamate for preparation of pH-sensitive functional groups. A case study

Click chemistry has became an important tool for molecular constructs such as biopolymers. During the development of biodegradable multifunctional poly(ethylene oxide) (PEO) polymers suitable for click chemistry in water, an unexpected reaction leading to a mixture of triazole cycloadducts was observed. This result was attributed to an intramolecular ligand effect, and alternative conditions were evaluated. An efficient method was then implemented allowing the access in high yields to the expected triazolylcarbamate. pH sensitivity of the obtained isopropyltriazolylcarbamate was demonstrated at acidic pH.     

基于喹啉和三唑环的开链冠醚对金属离子的选择传感

本文通过Click化学反应合成了一种含喹啉基和三唑基的开链冠醚, 考察和比较了主体化合物对镉等金属离子的荧光传感和选择性键合行为, 并通过荧光和核磁等手段研究了溶剂对其荧光传感的影响.     

Catalytic "active-metal" template synthesis of [2]rotaxanes, [3]rotaxanes, and molecular shuttles, and some observations on the mechanism of the cu(i)-catalyzed azide-alkyne 1,3-cycloaddition

A synthetic approach to rotaxane architectures is described in which metal atoms catalyze covalent bond formation while simultaneously acting as the template for the assembly of the mechanically interlocked structure. This "active-metal" template strategy is exemplified using the Huisgen-Meldal-Fokin Cu(I)-catalyzed 1,3-cycloaddition of azides with terminal alkynes (the CuAAC "click" reaction). Coordination of Cu(I) to an endotopic pyridine-containing macrocycle allows the alkyne and azide to bind to metal atoms in such a way that the metal-mediated bond-forming reaction takes place through the cavity of the macrocycle--or macrocycles--forming a rotaxane. A variety of mono- and bidentate macrocyclic ligands are demonstrated to form [2]rotaxanes in this way, and by adding pyridine, the metal can turn over during the reaction, giving a catalytic active-metal template assembly process. Both the stoichiometric and catalytic versions of the reaction were also used to synthesize more complex two-station molecular shuttles. The dynamics of the translocation of the macrocycle by ligand exchange in these two-station shuttles could be controlled by coordination to different metal ions (rapid shuttling is observed with Cu(I), slow shuttling with Pd(II)). Under active-metal template reaction conditions that feature a high macrocycle:copper ratio, [3]rotaxanes (two macrocycles on a thread containing a single triazole ring) are also produced during the reaction. The latter observation shows that under these conditions the mechanism of the Cu(I)-catalyzed terminal alkyne-azide cycloaddition involves a reactive intermediate that features at least two metal ions.     

Reactions of gaseous acylium ions with 1,3-dienes: further evidence for polar [4 + 2+] Diels-Alder cycloaddition

A novel reaction of acylium and thioacylium ions, polar [4 + 2(+)] Diels-Alder cycloaddition with 1,3-dienes and O-heterodienes, has been systematically investigated in the gas phase (Eberlin MN, Cooks RG. J. Am. Chem. Soc. 1993; 115: 9226). This polar cycloaddition, yet without precedent in solution, likely forms cyclic 2,5-dihydropyrylium ions. Here we report the reactions of gaseous acylium ions [(CH(3))(2)N-C(+)=O, Ph-C(+)=O, (CH(3))(2)N-C(+)=S, CH(3)-C(+)=O, CH(3)CH(2)-C(+)=O, and CH(2)=CH-C(+)=O] with several 1-oxy-substituted 1,3-dienes of the general formula RO-CH=CH-C(R(1))=CH(2), which were performed to collect further evidence for cycloaddition. In reactions with 1-methoxy and 1-(trimethylsilyloxy)-1,3-butadiene, adducts are formed to a great extent, but upon collision activation they mainly undergo structurally unspecific retro-addition dissociation. In reactions with Danishefsky's diene (trans-1-methoxy-3-(trimethylsilyloxy)-1,3-butadiene), adducts are also formed to great extents, but retro-addition is no longer their major dissociation; the ions dissociate instead mainly to a common fragment, the methoxyacryl cation of m/z 85. This fragment ion is most likely formed with the intermediacy of the acyclic adduct, which isomerizes prior to dissociation by a trimethylsilyl cation shift. Theoretical calculations predict that meta cycloadducts bearing 1-methoxy and 1-trimethylsilyloxy substituents are unstable, undergoing barrierless ring opening induced by the charge-stabilizing effect of the 1-oxy substituents. In contrast, for the reactions with 1-acetoxy-1,3-butadiene, both the experimental results and theoretical calculations point to the formation of intrinsically stable cycloadducts, but the intact cycloadducts are either not observed or observed in low abundances. Both the isomeric ortho and meta cycloadducts are likely formed, but the nascent ions dissociate to great extents owing to excess internal energy. The ortho cycloadducts dissociate by ketene loss; the meta cycloadducts undergo intramolecular proton transfer to the acetoxy group followed by dissociation by acetic acid loss to yield aromatic pyrylium ions. Either or both of these dissociations, ketene and/or acetic acid loss, dominate over the otherwise favored retro-Diels-Alder alternative. The pyrylium ion products therefore constitute compelling evidence for polar [4 + 2(+)] cycloaddition since their formation can only be rationalized with the intermediacy of cyclic adducts.     

Synthesis of sialoclusters appended to calix[4]arene platforms via multiple azide-alkyne cycloaddition. New inhibitors of hemagglutination and cytopathic effect mediated by BK and influenza A viruses

Tetra- and octavalent sialoside clusters were prepared in good yields exploiting for the first time the multiple copper-catalyzed cycloaddition of a propargyl thiosialoside with calix[4]arene polyazides. The cycloadducts featured the hydrolytically stable carbon-sulfur bond at the anomeric position and the 1,4-disubstituted triazole ring as the spacer between the sialic acid moieties and the platform. It was demonstrated that these unnatural motifs did not hamper the desired biological activity of the sialoclusters. In fact, they were able to inhibit, at submillimolar concentrations, the hemagglutination and the viral infectivity mediated both by BK and influenza A viruses.     

三唑类超分子化学与药物研究新进展

三唑环为含有三个氮原子的五元杂环, 唑环具有芳香性和丰富的电子, 易接受质子和络合金属离子, 因而三唑类化合物易通过配位键、氢键、离子-偶极、阳离子-?、?-?堆积、疏水效应以及范德华力等非共价键力形成超分子聚集体, 表现出许多特殊的性能及生物活性, 具有广泛的潜在应用如作为离子受体、材料、医药等. 近些年来, 相关三唑类超分子化学与医药的研究非常活跃, 发展特别迅速, 已成为十分活跃的热点研究领域. 本文结合自己的工作, 参考国内外近五年文献, 首次系统综述了三唑类化合物作为阳离子和阴离子受体以及三唑类超分子作为发光与磁性材料、医药在抗菌、抗真菌、抗癌等方面的研究与开发近况. 希望本综述对三唑类超分子化学与药物的进一步研发有所启迪.     

Regioselective synthesis of spiropyrrolidine/spiropyrrolizidine/spirothiazolidine-grafted macrocycles through 1,3-dipolar cycloaddition methodology

Synthesis of 13- and 16-membered macrocyclic enone with alkyl ether and triazole as a linker was achieved using intramolecular aldol condensation. The newly synthesized macrocyclic enone was successfully utilized as a dipolarophile in 1,3-dipolar cycloaddition (1,3-DC). The dipole generated from isatin/acenaphthenequinone with various secondary amino acids (sarcosine, l-proline, and thiazolidine-4-carboxylic acid) were reacted with macrocyclic enone to give a new class of spiropyrrolidine-grafted macrocycles in good yield (>85%). The structures were assigned by 2D NMR spectra and the regio- and stereochemical outcome of the cycloadducts were established by a single crystal X-ray analysis.     

Transition-metal-catalyzed denitrogenative transannulation: converting triazoles into other heterocyclic systems

Transition metal catalyzed denitrogenative transannulation of a triazole ring has recently received considerable attention as a new concept for the construction of diverse nitrogen-containing heterocyclic cores. This method allows a single-step synthesis of complex nitrogen heterocycles from easily available and cheap triazole precursors. In this Minireview, recent progress of the transition metal catalyzed denitrogenative transannulation of a triazole ring, which was discovered in 2007, is discussed.     

Synthesis,crystal structure and complexation behaviour of a thiacalix[4]arene bearing 1,2,3-triazole groups

The structure and complexation behaviour of 1,3-alternate-1,2,3-triazole based on thiacalix[4]arene,1,3-alternate-1 and 2 have been determined by means of X-ray analysis, fluorescence and ¹H NMR spectroscopy. The X-ray results suggested that the nitrogen atom N3 on triazole ring can act as hydrogen bond acceptors in the self-assembly of a supramolecular structure. The fluorescence spectra changes indicated that the thiacalix[4]arene bearing 1,2,3-triazole groups were highly selective for Ag⁺ in comparison with other tested metal ions by enhancement of the monomer emission of pyrene. The ¹H NMR results suggested that Ag⁺ can be strongly bonded by the triazole groups with the cooperation of the ionophoric cavity formed by the two inverted benzene rings and the sulfur atoms of the thiacalix[4]arene.     

Calcium and strontium,and zinc (phenazine)−· species

Calcium and strontium react with phenazine in tetrahydrofuran (THF) at ca 20 ° C to yield red solutions containing paramagnetic species based on (phenazine)⁻· (ESR characterization). Zinc reacts in THF in the presence of zinc chloride or bromide, or without metal halide in pyridine, to yield green or red ESR-active solutions also based on (phenazine)⁻·, and then, for the reaction in pyridine, a brown paramagnetic solid of composition Zn(phenazine)(pyridine)₂.