- Transient resonance Raman and density functional theory investigation of 4-methoxyphenylnitrenium and 4-ethoxyphenylnitrenium ions
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This paper presents a transient resonance Raman and density functional theory study of 4-methoxyphenylnitrenium and 4-ethoxyphenylnitrenium ions in a largely aqueous environment. The transient Raman bands observed in conjunction with the (U)BPW91/cc-PVDZ
- Chan, Pik Ying,Ong, Shing Yau,Zhu, Peizhi,Zhao, Cunyuan,Phillips, David Lee
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- 1,2,3-triazole-thiazole hybrids: Synthesis, in vitro antimicrobial activity and antibiofilm studies
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A new series of triazole-thiazole hybrids were designed, synthesized by the Multi-component reaction approach and evaluated in vitro antimicrobial activity. Most of the tested series of compounds exhibited promising inhibitory activity against the bacteri
- Gondru, Ramesh,Kanugala, Sirisha,Raj, Sneha,Ganesh Kumar,Pasupuleti, Mukesh,Banothu, Janardhan,Bavantula, Rajitha
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- Photochemistry of Aryl Pentazoles: Para -Methoxyphenylpentazole
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The photolysis of para-methoxyphenyl pentazole (MeOPP) in methylcyanide (MeCN), investigated in the far UV (FUV) and near UV (NUV) is compared with the photolysis of para-methoxyphenyl azide (MeOPA). The main photoproduct of MeOPP is MeOPA, which, due to
- Geiger,Haas
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- The race for the first generation of the pentazolate anion in solution is far from over
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The previous claim for the first generation of the pentazolate anion in solution was carefully reexamined; no evidence for the formation of cyclo-N 5- was found under the reported conditions. The Royal Society of Chemistry 2005.
- Schroer, Thorsten,Haiges, Ralf,Schneider, Stefan,Christe, Karl O.
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- Helicenoid-based bis-1,2,3-triazole tweezer: Synthesis and selective iodide sensing
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Novel helicenoid based 1,2,3-triazole tweezer 4 was synthesized using a multistep synthetic protocol with high yields from 2,7-Dihydroxynaphtlene 3 as a precursor. This helicenoid-based bis-1,2,3-triazole tweezer 4 selectively causes non-covalent interact
- Kamble, Siddharth B.,Gawade, Prashant M.,Badani, Purav M.,Karnik, Anil V.
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- Combinatorial synthesis of new fluorescent scaffolds using click chemistry
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Azides and acetylenes are bio-orthogonal functional groups that can be readily coupled using copper(I)- or ruthenium(II)- catalyzed 1,3-dipolar cycloaddition reactions. Using non-fluorescent aromatic azides and aromatic acetylenes, covering a range of electron rich and poor building blocks, the Huisgen cycloaddition afford 1,4-disubstituted or 1,5-disubstituted 1,2,3-triazoles. Using a combinatorial approach by running reaction in parallel in polypropylene 96-well plates we discovered several new fluorescent 1,2,3-triazoles scaffolds. These compounds show diverse interactions with biomolecules that could find applications in biology in, for example, fluorescence microscopy or biomolecule quantification.
- Cleemann, Felix,Karuso, Peter,Kum-Cheung, Wendy Loa
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supporting information
(2021/12/08)
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- Nickel Boride Catalyzed Reductions of Nitro Compounds and Azides: Nanocellulose-Supported Catalysts in Tandem Reactions
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Nickel boride catalyst prepared in situ from NiCl2 and sodium borohydride allowed, in the presence of an aqueous solution of TEMPO-oxidized nanocellulose (0.01 wt%), the reduction of a wide range of nitroarenes and aliphatic nitro compounds. Here we describe how the modified nanocellulose has a stabilizing effect on the catalyst that enables low loading of the nickel salt pre-catalyst. Ni-B prepared in situ from a methanolic solution was also used to develop a greener and facile reduction of organic azides, offering a substantially lowered catalyst loading with respect to reported methods in the literature. Both aromatic and aliphatic azides were reduced, and the protocol is compatible with a one-pot Boc-protection of the obtained amine yielding the corresponding carbamates. Finally, bacterial crystalline nanocellulose was chosen as a support for the Ni-B catalyst to allow an easy recovery step of the catalyst and its recyclability for new reduction cycles.
- Proietti, Giampiero,Prathap, Kaniraj Jeya,Ye, Xinchen,Olsson, Richard T.,Dinér, Peter
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supporting information
p. 133 - 146
(2021/11/04)
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- Discovery of new tranylcypromine derivatives as highly potent LSD1 inhibitors
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Tranylcypromine (TCP)-based structural modifications lead to the discovery of new LSD1 inhibitors, of which compounds 26b and 29b effectively inhibit LSD1 with the IC50 values of 17 and 11 nM, respectively and also show good selectivity over MAO-B. Mechanistic studies showed that compound 29b concentration-dependently induced H3K4me1/2 accumulation in LSD1 overexpressed MGC-803 cells and also inhibited metastasis of MGC-803 cells. Collectively, both compounds could be promising lead compounds for further investigation.
- Huang, Ming-Jie,Guo, Jia-Wen,Fu, Yun-Dong,You, Ya-Zhen,Xu, Wen-Yu,Song, Ting-Yu,Li, Ran,Chen, Zi-Tong,Huang, Li-Hua,Liu, Hong-Min
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supporting information
(2021/04/12)
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- New inha inhibitors based on expanded triclosan and di-triclosan analogues to develop a new treatment for tuberculosis
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The emergence of multidrug-resistant (MDR) and extensively drug-resistant (XDR) tuberculosis (TB) has reinforced the need for the development of new anti-TB drugs. The first line drug isoniazid inhibits InhA. This is a prodrug requiring activation by the enzyme KatG. Mutations in KatG have largely contributed to clinical isoniazid resistance. We aimed to design new ‘direct’ InhA inhibitors that obviate the need for activation by KatG, circumventing pre-existing resistance. In silico molecular modelling was used as part of a rational structure-based drug-design approach involving inspection of protein crystal structures of InhA:inhibitor complexes, including the broad spectrum antibiotic triclosan (TCS). One crystal structure exhibited the unusual presence of two triclosan molecules within the Mycobacterium tuberculosis InhA binding site. This became the basis of a strategy for the synthesis of novel inhibitors. A series of new, flexible ligands were designed and synthesised, expanding on the triclosan structure. Low Minimum Inhibitory Concentrations (MICs) were obtained for benzylphenyl compounds (12, 43 and 44) and di-triclosan derivative (39), against Mycobacterium bovis BCG although these may also be inhibiting other enzymes. The ether linked di-triclosan derivative (38) displayed excellent in vitro isolated enzyme inhibition results comparable with triclosan, but at a higher MIC (125 μg mL?1 ). These compounds offer good opportunities as leads for further optimisation.
- Chetty, Sarentha,Armstrong, Tom,Sharma Kharkwal, Shalu,Drewe, William C.,De Matteis, Cristina I.,Evangelopoulos, Dimitrios,Bhakta, Sanjib,Thomas, Neil R.
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- A general procedure for carbon isotope labeling of linear urea derivatives with carbon dioxide
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Carbon isotope labeling is a traceless technology, which allows tracking the fate of organic compounds either in the environment or in living organisms. This article reports on a general approach to label urea derivatives with all carbon isotopes, including14C and11C, based on a Staudinger aza-Wittig sequence. It provides access to all aliphatic/aromatic urea combinations.
- Babin, Victor,Sallustrau, Antoine,Loreau, Olivier,Caillé, Fabien,Goudet, Amélie,Cahuzac, Hélo?se,Del Vecchio, Antonio,Taran, Frédéric,Audisio, Davide
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supporting information
p. 6680 - 6683
(2021/07/12)
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- Design and synthesis of novel diosgenin-triazole hybrids targeting inflammation as potential neuroprotective agents
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Alzheimer's disease is a progressive neurodegenerative disease, and its incidence is expected to increase as the global population ages. Recent studies provide increasing evidence that inflammation plays a key role in the pathogenesis and progression of AD. Diosgenin, an active ingredient in Dioscorea nipponica Makino, is a promising bioactive lead compound in the treatment of Alzheimer's disease, which exhibited anti-inflammatory activity. To search for more efficient anti-Alzheimer agents, a series of novel diosgenin-triazolyl hybrids were designed, synthesized, and their neuroprotective effects against oxygen-glucose deprivation-induced neurotoxicity and LPS-induced NO production were evaluated. Most of these new hybrids displayed better activities than DIO. In particular, the promising compound L6 not only demonstrated an excellent neuroprotective effect but also showed the best anti-inflammatory activity. The structure-activity relationship study illustrated that the introduction of benzyl or phenyl triazole did improve the activity, and the introduction of benzyl triazole was better than that of phenyl triazole. The results we obtained showed that the diosgenin skeleton could be a promising structural template for the development of new anti-Alzheimer drug candidates, and compound L6 has the potential to be an important lead compound for further research.
- Huang, Yi,Huang, Weiwei,Yang, Guixiang,Wang, Rui,Ma, Lei
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supporting information
(2021/05/21)
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- Synthesis and antitumor activity of 1-substituted 1,2,3-triazole-mollugin derivatives
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A new series of mollugin-1,2,3-triazole derivatives were synthesized using a copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction of corresponding O-propargylated mollugin with aryl azides. All the compounds were evaluated for their cytotoxicity on five human cancer cell lines (HL-60, A549, SMMC-7721, SW480, and MCF-7) using MTS assays. Among the synthesized series, most of them showed cytotoxicity and most of all, compounds 14 and 17 exhibited significant cytotoxicity of all five cancer cell lines.
- Hu, Jiang-Miao,Li, Hong-Mei,Liu, Shou-Jin,Luo, Han,Lv, Yong-Feng,Zhang, Hong
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- Cycloaddition Reactions of Azides and Electron-Deficient Alkenes in Deep Eutectic Solvents: Pyrazolines, Aziridines and Other Surprises
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The reaction of organic azides and electron-deficient alkenes was investigated in a deep eutectic solvents. A series of highly substituted 2-pyrazolines was successfully isolated and their formation rationalised by DFT calculations. The critical effect of substitution was also explored; even relatively small changes in the cycloaddition partners led to completely different reaction outcomes and triazolines, triazoles or enaminones can be formed as major products depending on the alkene employed. (Figure presented.).
- Casarrubios, Luis,Díez-González, Silvia,Lachhani, Kushal,Pimpasri, Chaleena,Rzepa, Henry S.,Sebest, Filip,White, Andrew J. P.
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supporting information
(2020/05/19)
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- Derivative containing aromatic ring/aromatic heterocycle-triazole-methylene-TCP and preparation method and application thereof
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The invention discloses a derivative containing aromatic ring/aromatic heterocycle-triazole-methylene-TCP, which has a structure shown in a general formula I, has remarkable biological inhibition activity on LSD1, can be used for preparing a medicine for inhibiting LSD1, enriches the variety of TCP derivatives, and lays a foundation for researching and developing a novel LSD1 inhibitor. Particularly, the derivative can be used for preparing anti-tumor medicines, has a certain inhibition effect on a plurality of tumor cell strains such as gastric cancer cell strains (MGC-803, SGC-7901), breastcancer cell strains (MCF-7) and prostate cancer cell strains (PC-3), shows antitumor activity, provides a lead compound structure for anticancer drugs, and has a good application prospect. The invention also provides a preparation method of the aromatic ring/aromatic heterocycle-triazole-methylene-TCP containing derivative, (1R, 2S)-phenylcyclopropylamine or (1R, 2S)-3, 4-difluorophenylcyclopropylamine is used as a raw material, the derivative is prepared through alkyne feeding and cycloaddition reactions, the preparation method is simple, and batch production and commercial application are facilitated.
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Paragraph 0077; 0080
(2020/08/09)
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- Regioselective synthesis of 4-fluoro-1,5-disubstituted-1,2,3-triazoles from synthetic surrogates of α-fluoroalkynes
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α-Fluoroalkynes are elusive molecules due to their instability and inaccessibility. Here, we show that α-fluoronitroalkenes can serve as synthetic surrogates of α-fluoroalkynes in [3+2] cycloaddition reactions with organic azides facilitated by a catalytic amount of trifluoroacetic acid (TFA). This work provides the first regioselective method to access 4-fluoro-1,5-disubstituted-1,2,3-triazoles.
- Jana, Sampad,Adhikari, Sweta,Cox, Michael R.,Roy, Sudeshna
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supporting information
p. 1871 - 1874
(2020/02/20)
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- A Metal-Free Synthesis of N-Aryl Oxazolidin-2-Ones by the One-Pot Reaction of Carbon Dioxide with N-Aryl Aziridines
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The cost-effective TPPH2/TBACl-catalyzed (TPPH2=dianion of tetraphenyl porphyrin; TBACl=tetrabutyl ammonium chloride) carbon dioxide cycloaddition to N-aryl aziridines was successful in synthesizing N-aryl oxazolidin-2-ones. A cataly
- Sonzini, Paolo,Damiano, Caterina,Intrieri, Daniela,Manca, Gabriele,Gallo, Emma
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supporting information
p. 2961 - 2969
(2020/07/06)
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- Chan-Lam-type Azidation and One-Pot CuAAC under CuI-Zeolite Catalysis
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The copper(I)-exchanged zeolite CuI-USY proved to efficiently catalyze the direct azidation of arylboronic acids with sodium azide under simple and practical conditions, namely at room temperature under air with methanol as solvent and without any additive. This easy-to-prepare and cheap catalytic material has been demonstrated to be recyclable and the mild azidation conditions further showed good functional-group tolerance, leading to a variety of substituted (hetero)aryl azides (18 examples). Interestingly, the azidation reaction has been successfully coupled to a CuAAC reaction, thus allowing access to triazoles from arylboronic acids via a one-pot CuI-catalyzed process.
- Clerc, Arnaud,Bénéteau, Valérie,Pale, Patrick,Chassaing, Stefan
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p. 2060 - 2065
(2020/03/03)
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- New α-Hydroxy-1,2,3-triazoles and 9H-Fluorenes-1,2,3-triazoles: H Synthesis and Evaluation as Glycine Transporter 1 Inhibitors
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Two series of new compounds containing 1,2,3-triazole moiety were designed as putative GlyT1 inhibitors aiming the discovery of new hits with activity in cognitive disorders. 1,4-Disubstituted α-hydroxy-1,2,3-triazoles were obtained as racemates in moderate to good yields by the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction (click chemistry) as the key step between propargyl alcohols and aryl azides, previously prepared from anilines or boronic acids. Benzo[c]chromene-triazoles were planned to be obtained by palladium-catalyzed C?H activation using [bis(trifluoroacetoxy)iodobenzene] (PhI(TFA)2) of some α-hydroxy-1,2,3-triazoles, since benzo[c]chromenes are also privileged groups with several biological activities, including to the central nervous system. Unexpectedly, 9H-fluorenes-1,2,3-triazoles, instead of benzo[c]chromenetriazoles, were obtained by Friedel-Crafts alkylation reaction. The two series of compounds were tested for inhibition of the glycine transporter (rat GlyT1 isoform) but only the α-hydroxy-1,2,3-triazole 9b was active (half maximal inhibitory concentration (IC50) = 8.0 μM).
- Buarque, Camilla D.,Guimar?es, Marilia Z.,López?Corcuera, Beatriz,Neto, Jo?o Gon?alves,No?l, Fran?ois,Silva, Rafaela R.,da Silva, Veronica D.
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p. 1258 - 1269
(2020/10/14)
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- Efficient and simple synthesis of novel 1,2,3-triazolyl-linked benzimidazolone, molecular docking and evaluation of their antimicrobial activity
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In this study, a novel series of 1,2,3-triazolyl-benzimidazolone derivatives have been synthesized by click reaction of azides with benzimidazolones 2a–b. The latter compounds were prepared with excellent yields (85–97%), the structures of products were determined by spectral analysis. Then, the X-rays crystallographic analysis of compound 7a revealed the self-assembling properties. The new heterocycles were evaluated for their in?vitro antimicrobial activities against Gram-positive and Gram-negative bacteria and against fungi strains. The most tested synthesized compounds showed potent antibacterial and antifungal activities against all tested strains. The compound 6c was found to be the most active, particularly, against Aspergillus niger and Penicillium sp. with the same MIC and MBC of 0.0625 mg/mL. Furthermore, in silico molecular docking studies stipulated a sign of a good correlation between experimental activity and calculated binding affinity. According to the docking results, compound 6d showed minimum binding energy and can be considered as a good antimicrobial agent.
- Adardour, Mohamed,Boutafda, Aziz,Hdoufane, Ismail,Aghraz, Abdellah,Hafidi, Mohamed,Zaballos-García, Elena,Cherqaoui, Driss,Baouid, Abdesselam
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p. 3490 - 3506
(2020/08/19)
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- Design, synthesis and biological evaluation of new steroidal β-triazoly enones as potent antiproliferative agents
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β-Triazoly enones are biologically interesting scaffolds, incorporation of such scaffolds into the steroid nucleus may generate new bioactive steroids and further enrich structural types of steroids. In this work, a series of new steroidal β-triazoly enon
- Zhao, Jian-Wei,Guo, Jia-Wen,Huang, Ming-Jie,You, Ya-Zhen,Wu, Zeng-Hui,Liu, Hong-Min,Huang, Li-Hua
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supporting information
(2019/07/12)
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- Facile immobilization of copper(I) acetate on silica: A recyclable and reusable heterogeneous catalyst for azide–alkyne clickable cycloaddition reactions
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The structurally well-defined copper(I) acetate was immobilized on silica gel via electrostatic interactions. The catalytic activity of the immobilized catalyst Cu(I)–SiO2 was examined in the click synthesis of 1,2,3-triazoles in water/ethanol
- Aflak,El Ayouchia, Hicham Ben,Bahsis, Lahoucine,Anane,Laamari, Rachid,Pascual-Alvarez, Alejandro,Armentano, Donatella,Stiriba, Salah-Eddine
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p. 630 - 638
(2019/07/10)
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- 16-(1'-aryl-1',2',3'-triazole)methylene-androst-17-ketone derivative
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The invention belongs to the technical field of drug chemistry, and relates to a 16-(1'-aryl-1',2',3'-triazole)methylene-androst-17-ketone derivative as well as a preparation method and application thereof. The compound has the following general formula:
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Paragraph 0057; 0059; 0060
(2019/02/04)
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- Design, synthesis and anti-platelet aggregation activity study of ginkgolide-1,2,3-triazole derivatives
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Ginkgolides are the major active component of Ginkgo biloba for inhibition of platelet activating factor receptor. An azide-alkyne Huisgen cycloaddition reaction was used to introduce a triazole nucleus into the target ginkgolide molecules. A series of ginkgolide-1,2,3-triazole conjugates with varied functional groups including benzyl, phenyl and heterocycle moieties was thus synthesized. Many of the designed derivatives showed potent antiplatelet aggregation activities with IC50 values of 5~21 nM.
- Cui, Jian,Hu, Lean,Shi, Wei,Cui, Guozhen,Zhang, Xumu,Zhang, Qing-Wen
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- Iron and Ruthenium Glycoporphyrins: Active Catalysts for the Synthesis of Cyclopropanes and Aziridines
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In view of the relevance of cyclopropanes and aziridines as synthetic building blocks as well as active parts in biological and pharmaceutical compounds, the development of sustainable synthetic procedures for obtaining these products continues to be a si
- Damiano, Caterina,Gadolini, Sebastiano,Intrieri, Daniela,Lay, Luigi,Colombo, Cinzia,Gallo, Emma
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supporting information
p. 4412 - 4420
(2019/11/03)
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- Cleavage of C(aryl)?CH3 Bonds in the Absence of Directing Groups under Transition Metal Free Conditions
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Organic chemists now can construct carbon–carbon σ-bonds selectively and sequentially, whereas methods for the selective cleavage of carbon–carbon σ-bonds, especially for unreactive hydrocarbons, remain limited. Activation by ring strain, directing groups, or in the presence of a carbonyl or a cyano group is usually required. In this work, by using a sequential strategy site-selective cleavage and borylation of C(aryl)?CH3 bonds has been developed under directing group free and transition metal free conditions. Methyl groups of various arenes are selectively cleaved and replaced by boryl groups. Mechanistic analysis suggests that it proceeds by a sequential intermolecular oxidation and coupling of a transient aryl radical, generated by radical decarboxylation, involving a pyridine-stabilized persistent boryl radical.
- Dai, Peng-Fei,Ning, Xiao-Shan,Wang, Hua,Cui, Xian-Chao,Liu, Jie,Qu, Jian-Ping,Kang, Yan-Biao
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p. 5392 - 5395
(2019/03/29)
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- Synthesis, structure, and synthetic potential of arenediazonium trifluoromethanesulfonates as stable and safe diazonium salts
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Aromatic diazonium salts are valuable building blocks for organic synthesis; however, in most cases, they are unstable, unsafe, poorly soluble, and/or expensive. In this paper, we have shown that a variety of stable and safe arenediazonium triflates ArN2+ TfO– can be obtained easily and in high yields by diazotization of anilines with tert-butyl nitrite in the presence of trifluoromethanesulfonic acid. Arenediazonium triflates are relatively shelf-stable in the dry state. They dissolve well in water, as well as polar and even nonpolar organic solvents. Less than 800 J/g of energy is released during the thermal decomposition of these salts, which indicates their explosion safety. Arenediazonium triflates have a high reactivity in the known reactions of diazonium chemistry, and undergo an unusual metal-free chlorodediazonization reaction with chloroform and CCl4.
- Filimonov, Victor D.,Krasnokutskaya, Elena A.,Kassanova, Assia Zh.,Fedorova, Valentina A.,Stankevich, Ksenia S.,Naumov, Nikolay G.,Bondarev, Alexander A.,Kataeva, Veronika A.
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supporting information
p. 665 - 674
(2018/09/14)
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- RETRACTED ARTICLE: Synthesis, Molecular Properties, and Biological Evaluation of Hybrid 1,2,3-Triazolylpolyaza Heterocyclic Compounds
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In this research article, a highly efficient, cost-effective synthesis of various hybrid molecules possessing 1,2,3-triazolyltetrazoles and evaluation of their biological activity have been addressed. The structure elucidation of these new library hybrid molecules has been carried out by IR, 1H NMR, 13C NMR, and mass spectral analysis. The compounds have been screened for their anticancer activity against human colon cancer cell line Colo-205 and human lung cancer cell line HOP-205, and the results attest that most of the compounds have shown very good therapeutic nature. In particular, compounds 3d, 3j, 6a, and 6e were more cytotoxic than Adriamycin against all tested human cancer cell lines with 68percent, 101.8percent, 94percent, and 104.5percent growth, respectively. In the present investigation, a series of 3a–j and 6a–h were subjected to molecular properties prediction, drug likeness by Molinspiration, and toxicity risks by Molsoft software programs. All the 18 analogues were chosen on the basis of Lipinski “Rule of five” for the synthesis, screening their antibacterial and anticancer as oral bioavailable drugs/leads.
- Dasari, Srinivasa Rao,Tondepu, Subbaiah,Vadali, Lakshmana Rao,Ganivada, Mutyala Naidu,Seelam, Nareshvarma
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p. 195 - 208
(2019/01/04)
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- Investigating the Impact of Conformational Molecular Engineering on the Crystal Packing of Cavity Forming Porphyrins
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Herein we report the synthesis of 5,10,15,20-tetraaryl-(X)-substituted-2,3,7,8,12,13,17,18-octaethylporphyrins (OETArXPs) and a structural investigation of their solid-state properties via small molecule X-ray diffraction. A series of halogen (fluorine to iodine), nitrogenous (azido, cyano), alkyl (TMS-acetylene and acetylene), and chained (benzyloxy) porphyrins were chosen as the initial target molecules. Following this, a selection of tetravalent metal complexes [Cu(II), Ni(II), and Pd(II)] based on these porphyrins were synthesized to allow for an investigation of the effects of metal complexes on the structural properties of these highly substituted porphyrins. The size of the halogen atom affects the potential of intermolecular interactions and the resulting crystal packing in these 4-halo-OETArXP complexes. The fluorine series have an equal preference for alkyl or aryl groups (ortho-hydrogen), the chlorine series favor interactions between the alkyl groups, and the bromine appears to favor the aryl (ortho- and meta-hydrogens). This results in an extensive cupping pattern in the unit cell. For the 2,6-halo-OETArXP it was established that the change in position alters the types of the intermolecular contacts toward face-to-edge or face-to-face interactions and alters the packing patterns observed. Within the 4-benzyloxy-OETArXP series the meso-substituent favors interacting with the core of the porphyrin macrocycle. The 4-cyano-OETArXP is a suitable hydrogen-bond acceptor and results in an interesting Z-shape network. Additionally, it was highlighted that solvent effects play a much larger role in crystal packing than intermolecular/intramolecular interaction or metal(II) center substitution. This is accompanied by a study using both the azide- and acetylene-OETArXPs as a base molecule to allow for a quick one-step reaction for the generation of a variety of functionalized compounds. Using a copper(I)-catalyzed azide-alkyne cycloaddition reaction, we were able to append hydrogen bonding functionalities to the OETArXPs framework in high yields. The crystal packing images included in this work shows the potential to create selective and functional receptor sites based on free base porphyrins. However, insofar as analytical measurements indicate, the design of such a free base porphyrin through crystal engineering has not yet been realized. The variety of porphyrin packing arrangements herein indicates the need for further studies.
- Flanagan, Keith J.,Twamley, Brendan,Senge, Mathias O.
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p. 15769 - 15787
(2019/12/11)
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- Identification of highly potent and selective Cdc25 protein phosphatases inhibitors from miniaturization click-chemistry-based combinatorial libraries
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Cell division cycle 25 (Cdc25) protein phosphatases play key roles in the transition between the cell cycle phases and their association with various cancers has been widely proven, which makes them ideal targets for anti-cancer treatment. Though several Cdc25 inhibitors have been developed, most of them displayed low activity and poor subtype selectivity. Therefore, it is extremely important to discover novel small molecule inhibitors with potent activities and significant selectivity for Cdc25 subtypes, not only served as drugs to treat cancer but also to probe its mechanism in transitions. In this study, miniaturized parallel click chemistry synthesis via CuAAC reaction followed by in situ biological screening were used to discover selective Cdc25 inhibitors. The bioassay results showed that compound M2N12 proved to be the most potent Cdc25 inhibitor, which also act as a highly selective Cdc25C inhibitor and was about 9-fold potent than that of NSC 663284. Moreover, M2N12 showed remarkable anti-growth activity against the KB-VIN cell line, equivalent to that of PXL and NSC 663284. An all-atom molecular dynamics (MD) simulation approach was further employed to probe the significant selectivity of M2N12 for Cdc25C relative to its structural homologs Cdc25A and Cdc25B. Overall, above results make M2N12 a promising lead compound for further investigation and structural modification.
- Jing, Lanlan,Wu, Gaochan,Hao, Xia,Olotu, Fisayo A.,Kang, Dongwei,Chen, Chin Ho,Lee, Kuo-Hsiung,Soliman, Mahmoud E.S.,Liu, Xinyong,Song, Yuning,Zhan, Peng
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- A green route for the cross-coupling of azide anions with aryl halides under both base and ligand-free conditions: Exceptional performance of a Cu2O-CuO-Cu-C nanocomposite
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A convenient, inexpensive and effective route for the preparation of a Cu2O-CuO-Cu-C nanocomposite is described here by applying Cu(ii) as a source of copper. Characterization of the nanocomposite was performed with X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray spectroscopy (EDX). Analysis of the data showed that the particles of the nanocomposite are uniformly distributed and show high catalytic activity in the cross-coupling of sodium azide with various aryl iodides and bromides. This nanocomposite has a high level of performance, and even led to the synthesis of the products at room temperature. In addition, this is the first report of the synthesis of aryl azides under both base- and ligand-free conditions. For the first time, both ligand- and base-free conditions were applied for the synthesis of aryl azides, which implies exceptional performance of the Cu2O-CuO-Cu-C nanocomposite. Simultaneous removal of the base and ligand in a green solvent is the main advantage of this reaction. Unfortunately, aryl bromides and aryl iodides with electron-withdrawing functional groups in their scaffold did not give the desired aryl azides.
- Karimzadeh, Morteza,Niknam, Khodabakhsh,Manouchehri, Neda,Tarokh, Dariush
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p. 25785 - 25793
(2018/07/31)
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- Chloromethylated polystyrene supported copper (II) bis–thiazole complex: Preparation, characterization and its application as a heterogeneous catalyst for chemoselective and homoselective synthesis of aryl azides
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This work deals the synthesis of aryl azides catalyzed by heterogeneous copper (II) complex of 3,5–bis (2–benzothiazolyl) pyridine, [Cu (II)(BTP)(OTf)2], immobilized on chloromethylated polystyrene, [Cu (II)(BTP)(OTf)2]@CMP. The prepared catalyst was characterized by different analytical techniques such as X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (SEM), energy dispersive X–ray spectroscopy (EDX), elemental analysis, and FT-IR and UV–Vis spectroscopic methods. This catalytic system showed excellent activity in the synthesis of aryl azides by the reaction of aryl halides with sodium azide in the presence of catalytic amounts of [Cu (II)(BTP)(OTf)2]@CMP. Moreover, this unique catalyst could be recovered easily and reused several times without any considerable loss of its catalytic activity.
- Dehbanipour, Zahra,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj
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- DBU-promoted Cu(OAc)2·H2O-catalysed coupling reactions of aryl iodides and sodium azide
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An efficient and simple protocol for the synthesis of aryl azides by the coupling of aryl iodides with sodium azide, in good to excellent yields in DMSO at 95°C under catalysis by Cu(OAc)2·H2O and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), has been established. The optimised loadings of Cu(OAc)2·H2O and DBU were 10 mol% and 15 mol% respectively.
- Jiang, Yuqin,Suo, Huajun,Zhao, Yaru,Li, Xiyong,Sun, Yamin,Li, Xingfeng,Dong, Wenpei,Li, Wei,Zhang, Weiwei,Xu, Guiqing
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p. 247 - 250
(2018/06/29)
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- Controlled Transformations of Aryl Halides in a Flow System: Selective Synthesis of Aryl Azides and Aniline Derivatives
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Copper-mediated nitrogenation of aryl halides with sodium azide can result in either aryl azides or aniline derivatives. The selectivity of the transformation is highly dependent on reaction time and temperature, which led to contradictory literature results with respect to product selectivity and the conditions applied. The advantages of a strictly controlled flow reactor environment were exploited in order to facilitate selective haloarene transformations. Reaction conditions were carefully investigated to understand their role on product selectivity. Aryl azides and aryl amines were successfully prepared from the same starting materials using the same auxiliaries by means of precise control over residence time and reaction temperature, thereby ensuring time-, cost- and atom-efficient syntheses. (Figure presented.).
- Georgiádes, ádám,?tv?s, Sándor B.,Fül?p, Ferenc
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p. 1841 - 1849
(2018/04/09)
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- Thermal azide-Alkene cycloaddition reactions: straightforward multi-gram access to Δ2-1,2,3-Triazolines in deep eutectic solvents
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The multi-gram synthesis of a wide range of 1,2,3-Triazolines via azide-Alkene cycloaddition reactions in a Deep Eutectic Solvent (DES) is reported. The role of DES in this transformation as well as the origin of the full product distribution was studied with an experimental/computational-DFT approach.
- Sebest, Filip,Casarrubios, Luis,Rzepa, Henry S.,White, Andrew J. P.,Díez-González, Silvia
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supporting information
p. 4023 - 4035
(2018/09/11)
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- Phosphino-Triazole Ligands for Palladium-Catalyzed Cross-Coupling
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Twelve 1,5-disubtituted and fourteen 5-substituted 1,2,3-triazole derivatives bearing diaryl or dialkyl phosphines at the 5-position were synthesized and used as ligands for palladium-catalyzed Suzuki-Miyaura cross-coupling reactions. Bulky substrates wer
- Zhao, Yiming,Van Nguyen, Huy,Male, Louise,Craven, Philip,Buckley, Benjamin R.,Fossey, John S.
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supporting information
p. 4224 - 4241
(2018/10/25)
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- Waste-minimised copper-catalysed azide-alkyne cycloaddition in Polarclean as a reusable and safe reaction medium
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Herein we report the first example of a generally useful organic reaction, namely the copper-catalysed azide-alkyne cycloaddition, performed in a Polarclean/water mixture as a reaction medium. The process is very efficient, affording in 24 out of the 26 tested cases the desired triazole in quantitative yields. Product isolation is also very convenient, since the triazoles either precipitate or form a separate liquid phase, without the need to perform chromatographic separations. Moreover, since the metal catalyst is retained in the Polarclean/water phase, the catalyst/reaction medium can be easily reused for consecutive reaction runs, without an apparent loss in efficiency. This methodology is associated with very limited waste production, as evidenced by calculated E-factors in the range 2.6-3.7.
- Luciani, Lorenzo,Goff, Emily,Lanari, Daniela,Santoro, Stefano,Vaccaro, Luigi
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supporting information
p. 183 - 187
(2018/01/17)
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- Tuning the biological activity of cationic anthraquinone analogues specifically toward Staphylococcus aureus
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Development of new antibacterial agents against drug resistant bacteria is an imminent task, especially against methicillin-resistant Staphylococcus aureus (MRSA). While MRSA can still be treated with broad spectrum antibiotics, the use of which often leads to the disruption of normal microbial flora leading to Clostridium difficile infection (CDI). Herein, a new class of antibacterial agent, cationic anthraquinone analogues specifically against MRSA, has been developed. Through the variation and optimization of substituents, these agents are selective toward MRSA, and not Gram negative bacteria which may avoid the problem of CDI. In addition, newly discovered lead compounds also show significantly reduced cytotoxicity against normal mammalian cells than cancerous cells. This interesting finding can alleviate the toxicity and side effect problems often associate with the use of antibiotics.
- Subedi, Yagya Prasad,Alfindee, Madher N.,Shrestha, Jaya P.,Chang, Cheng-Wei Tom
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p. 683 - 690
(2018/08/23)
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- Design, synthesis, and structure-activity relationships of novel imidazo[4,5-c]pyridine derivatives as potent non-nucleoside inhibitors of hepatitis C virus NS5B
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The hepatitis C virus (HCV) NS5B polymerase is an attractive target for the development of novel and selective inhibitors of HCV replication. In this paper, the design, synthesis, and preliminary SAR studies of novel inhibitors of HCV NS5B polymerase based on the structure of tegobuvir have been described. The efforts to optimize the antiviral potency and reduce the treatment side effects with respect to genotype 1b resulted in the discovery of compound 3, which exhibited an EC50 of 1.163 nM and a CC50 >200 nM in a cell-based HCV replicon system assay. Additionally, testing for inhibition of the hERG channel showed a marked improvement over tegobuvir and the pharmacokinetic properties of compound 3 indicated that it was worthy of further investigation as a non-nucleoside inhibitor of HCV NS5B polymerase.
- Liu, Moyi,Xu, Qiaoling,Guo, Su,Zuo, Ruixi,Hong, Yue,Luo, Yong,Li, Yingxiu,Gong, Ping,Liu, Yajing
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p. 2621 - 2631
(2018/04/30)
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- Design, synthesis and anticancer biological evaluation of novel 1,4-diaryl-1,2,3-triazole retinoid analogues of tamibarotene (AM80)
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We report herein the design and synthesis via click chemistry of twelve novel triazole retinoid analogues of tamibarotene (AM80) and the evaluation of their anticancer activities against six cancer cell lines: HL60, K562, 786, HT29, MCF7 and PC3. Among the synthesized compounds, two were more potent than tamibarotene against solid tumor cells, and one of them had similar potency to tamibarotene against HL60 cells. The bioisosteric exchange between the amide group and the 1,2,3-triazole core in the retinoid agent tamibarotene (AM80) reported in this work is a valid strategy for the generation of useful compounds against cancer.
- Aleixo, Mariana A. A.,Garcia, Taís M.,Carvalho, Diego B.,Viana, Luiz H.,Amaral, Marcos S.,Kassab, Najla M.,Cunha, Marilin C.,Pereira, Indiara C.,Guerrero, Palimécio G,Perdomo, Renata T.,Matos, Maria F. C.,Baroni, Adriano C. M.
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p. 109 - 124
(2017/12/08)
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- Antitubercular Bis-Substituted Cyclam Derivatives: Structure-Activity Relationships and in Vivo Studies
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We recently reported the discovery of nontoxic cyclam-derived compounds that are active against drug-resistant Mycobacterium tuberculosis. In this paper we report exploration of the structure-activity relationship for this class of compounds, identifying
- Spain, Malcolm,Wong, Joseph K.-H.,Nagalingam, Gayathri,Batten, James M.,Hortle, Elinor,Oehlers, Stefan H.,Jiang, Xiao Fan,Murage, Hasini E.,Orford, Jack T.,Crisologo, Patrick,Triccas, James A.,Rutledge, Peter J.,Todd, Matthew H.
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p. 3595 - 3608
(2018/05/01)
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- Transient Protection of Organic Azides from Click Reactions with Alkynes by Phosphazide Formation
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A method for protecting organic azides from click reactions with alkynes is reported. Treatment of azides with Amphos affords phosphazides, which are stable under click reaction conditions and are easily converted back to azides by treatment with elemental sulfur. Thus, the method allows for facile modification of azide compounds via site-selective click reactions.
- Meguro, Tomohiro,Yoshida, Suguru,Igawa, Kazunobu,Tomooka, Katsuhiko,Hosoya, Takamitsu
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supporting information
p. 4126 - 4130
(2018/07/15)
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- Catalytic Azoarene Synthesis from Aryl Azides Enabled by a Dinuclear Ni Complex
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Azoarenes are valuable chromophores that have been extensively incorporated as photoswitchable elements in molecular machines and biologically active compounds. Here, we report a catalytic nitrene dimerization reaction that provides access to structurally and electronically diverse azoarenes. The reaction utilizes aryl azides as nitrene precursors and generates only gaseous N2 as a byproduct. By circumventing the use of a stoichiometric redox reagent, a broad range of organic functional groups are tolerated, and common byproducts of current methods are avoided. A catalyst featuring a Ni - Ni bond is found to be uniquely effective relative to those containing only a single Ni center. The mechanistic origins of this nuclearity effect are described.
- Powers, Ian G.,Andjaba, John M.,Luo, Xuyi,Mei, Jianguo,Uyeda, Christopher
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supporting information
p. 4110 - 4118
(2018/03/29)
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- Synthesis and antimicrobial activity of 4-substituted 1,2,3-triazole-coumarin derivatives
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A new series of coumarin-1,2,3-triazole conjugates with varied alkyl, phenyl and heterocycle moieties at C-4 of the triazole nucleus were synthesized using a copper(I)-catalysed Huisgen 1,3-dipolar cycloaddition reaction of corresponding O-propargylated coumarin (3) or N-propargylated coumarin (6) with alkyl or aryl azides. Based on their minimal inhibitory concentrations (MICs) against selected microorganisms, six out of twenty-six compounds showed significant antibacterial activity towards Enterococcus faecalis (MIC = 12.5–50 μg/mL). Moreover, the synthesized triazoles show relatively low toxicity against human erythrocytes.
- López-Rojas, Priscila,Janeczko, Monika,Kubiński, Konrad,Amesty, ángel,Mas?yk, Maciej,Estévez-Braun, Ana
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- Rhodium(I)-Catalyzed Azide-Alkyne Cycloaddition (RhAAC) of Internal Alkynylphosphonates with High Regioselectivities under Mild Conditions
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A regioselective method to access fully substituted 1,2,3-triazolyl-4-phosphonates from the internal alkynylphosphonates by rhodium(I)-catalyzed azide-alkyne cycloaddition (RhAAC) under mild conditions is reported. This approach is water and air compatible and has a broad substrate scope, good functional group tolerance, high yields and excellent regioselectivities. Fully substituted 1,2,3-triazolyl-4-phosphonates are directly prepared from the internal alkynylphosphonates by RhAAC with high 1,4-regioselectivities. The gram-scale preparation, application to carbohydrate synthesis and the solid-phase synthesis of triazolyl-4-phosphonates are highlights of this method. (Figure presented.).
- Song, Wangze,Zheng, Nan,Li, Ming,Ullah, Karim,Zheng, Yubin
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supporting information
p. 2429 - 2434
(2018/05/30)
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- Synthesis method for aryl azide compound
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The invention discloses a synthesis method for an aryl azide compound. The synthesis method includes the steps of: adding an iodo-aryl compound, sodium azide, 1,8-diazabicyclo[5.4.0]undecane-7-ene and a catalyst into a reaction container filled with a solvent, performing a stirring reaction to the reaction mixture at 60-105 DEG C with TLC tracing detection until the reaction is completed, adding ammonia water to the reaction mixture, extracting the reaction mixture for 3 times by ethyl acetate, washing the reaction mixture for 1 time by saturated salt water, drying an organic phase, performing suction filtration and spinning solvent removal, and performing column chromatographic purification to obtain a target product. The method employs easy-to-obtained raw materials and has wide selection range of copper source of the catalyst, has mild reaction condition, simple operation and high yield.
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-
Paragraph 0018; 0019
(2017/08/28)
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- Combining ethylenediamine and ionic liquid functionalities within SBA-15: A promising catalytic pair for tandem Cu–AAC reaction
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This paper discloses the assembly and characterization of an advanced heterogeneous catalyst formulated as CuI@SBA-15/PrEn/ImPF6. It is based on a mesoporous silica SBA-15 skeleton which bears a supported ethylenediamine/CuI complex and covalently anchored imidazolium/PF6 ionic liquid. This catalyst was successfully applied in tandem methods for triazole synthesis starting from different substrate pairs: aryl halides and aryl acetylenes (method A), arylboronic acids and aryl acetylenes (method B). The CuI@SBA-15/PrEn/ImPF6 catalyst showed high activity (up to 90% yields of triazole products under optimized reaction conditions), high stability and no appreciable leaching of CuI owing to its strong binding via the coordination with PrEn functionality. Therefore, the catalyst can be recycled for several consecutive runs (7–14 cycles) in this new synthetic method. For both methods A and B, specific types of green approaches were developed and the favorable products were produced in high yields.
- Hosseini, Habib Golchin,Doustkhah, Esmail,Kirillova, Marina V.,Rostamnia, Sadegh,Mahmoudi, Ghodrat,Kirillov, Alexander M.
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- Redox reaction between benzyl azides and aryl azides: concerted synthesis of aryl nitriles and anilines
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A unique and novel reaction between benzyl azides and aryl azides is described to synthesize aryl nitriles and anilines concurrently, which is catalyzed with a photoactivated diruthenium complex. N-Unsubstituted imines (N-H imines) are generated first from benzyl azides, followed by the hydrogen transfer reaction between N-H imines and aryl azides. A wide range of aryl nitriles and anilines were synthesized under neutral and mild reaction conditions.
- Kim, Yongjin,Rhee, Young Ho,Park, Jaiwook
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supporting information
p. 1636 - 1641
(2017/02/23)
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- Dual roles of substituted thiourea as reductant and ligand in CuAAC reaction
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A highly efficient catalytic system, CuSO4·5H2O/1-(4-methoxyphenyl)-3-phenylthiourea, for the copper(I)-catalyzed azide–alkyne cycloaddition reaction (CuAAC) was discovered. In the above catalytic system, substituted thiourea acts both as a reductant and a ligand. CuSO4·5H2O/1-(4-methoxyphenyl)-3-phenylthiourea is both an economical and efficient catalyst for the CuAAC reaction. In addition, the new catalytic system has advantageous features including mild and green reaction conditions, and broad substrate compatibility. A variety of 1,4-disubstituted 1,2,3-triazoles have been prepared with good to excellent yields with the CuSO4·5H2O/1-(4-methoxyphenyl)-3-phenylthiourea catalytic system in aqueous solution.
- Wang, Siyu,Jia, Kai,Cheng, Jiajia,Chen, Yu,Yuan, Yaofeng
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supporting information
p. 3717 - 3721
(2017/09/01)
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- A reliable one-pot synthesis of aryl azides from aryl amines using organotin azides as effective and recoverable reagents
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A mild and mass-efficient procedure based on the one-pot diazotization-azidodediazoniation of aromatic amines is described. A wide range of aryl azides are obtained in moderate to high yields by using tributyltin azide as an effective and reusable azide source in the presence of p-toluenesulfonic acid at room temperature. The method was also successfully applied employing an insoluble polymer-supported organotin azide.
- Godoy Prieto, Leonela,Lo Fiego, Marcos J.,Chopa, Alicia B.,Lockhart, María T.
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supporting information
p. 26 - 32
(2016/12/18)
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- Reaction of azides and enolisable aldehydes under the catalysis of organic bases and: Cinchona based quaternary ammonium salts
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Herein we report a two-step sequence for the preparation of amides starting from azides and enolisable aldehydes. The reaction proceeded via the formation of triazoline intermediates that were converted into amides via Lewis acid catalysis. Preliminary st
- Destro, Dario,Sanchez, Sandra,Cortigiani, Mauro,Adamo, Mauro F. A.
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supporting information
p. 5227 - 5235
(2017/07/11)
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- Small Molecule Microarray Based Discovery of PARP14 Inhibitors
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Poly(ADP-ribose) polymerases (PARPs) are key enzymes in a variety of cellular processes. Most small-molecule PARP inhibitors developed to date have been against PARP1, and suffer from poor selectivity. PARP14 has recently emerged as a potential therapeutic target, but its inhibitor development has trailed behind. Herein, we describe a small molecule microarray-based strategy for high-throughput synthesis, screening of >1000 potential bidentate inhibitors of PARPs, and the successful discovery of a potent PARP14 inhibitor H10 with >20-fold selectivity over PARP1. Co-crystallization of the PARP14/H10 complex indicated H10 bound to both the nicotinamide and the adenine subsites. Further structure–activity relationship studies identified important binding elements in the adenine subsite. In tumor cells, H10 was able to chemically knockdown endogenous PARP14 activities.
- Peng, Bo,Thorsell, Ann-Gerd,Karlberg, Tobias,Schüler, Herwig,Yao, Shao Q.
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supporting information
p. 248 - 253
(2016/12/30)
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- Hydrotrope promoted in situ azidonation followed by copper catalyzed regioselective synthesis of β-hydroxytriazoles
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Abstract: The rapid method for the synthesis of organic azides was achieved by employing azide acceptors such as halides, epoxides and pseudohalides like diazonium salts and aryl boronic acids in hydrotropic media. In extension, the sequential multicomponent reaction of epoxides, azide and alkynes using copper catalysis has been discussed. The reaction proceeds via the in situ generation of azido-alcohol followed by synthesis of chiral β-hydroxytriazoles. This [3?+?2] cycloaddition reaction of azide and alkyne using copper catalysis serves as a green and efficient protocol in “Click Chemistry”. The nucleophilic addition of azide to epoxide and alkyne-azide cycloaddition is the two simultaneous regioselective click reactions observed in the proposed method. Graphical Abstract: [Figure not available: see fulltext.].
- Patil, Amol,Salunkhe, Rajashri
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p. 4175 - 4187
(2017/06/20)
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- Selective C(sp2)-H Halogenation of "click" 4-Aryl-1,2,3-triazoles
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Selective bromination reactions of "click compounds" are described. Electron-neutral and electron-deficient arenes selectively undergo unprecedented Pd-catalyzed C-H ortho-halogenations assisted by simple triazoles as modular directing groups, whereas electron-rich arenes are regioselectively halogenated following an electrophilic aromatic substitution reaction pathway. These C-H halogenation procedures exhibit a wide group tolerance, complement existing bromination procedures, and represent versatile synthetic tools of utmost importance for the late-stage diversification of "click compounds". The characterization of a triazole-containing palladacycle and density functional theory studies supported the mechanism proposal.
- Goitia, Asier,Gómez-Bengoa, Enrique,Correa, Arkaitz
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supporting information
p. 962 - 965
(2017/02/26)
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