- Isolation of a labile homoleptic diazenium cation
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Following our interest in nitrogen chemistry, we now describe the synthesis, structure, and bonding of labile disilylated diazene, its GaCl 3 adduct, and the intriguing trisilylated diazenium ion [(Me 3Si)2Ni=N-SiMe3]+, a dark blue and highly labile (Tdecomp>-30 °C) homoleptic cation of the type [R3N2]+. Although direct silylation of Me 3Si-Ni=N-SiMe3 failed, the [(Me3Si) 2Ni=N-SiMe3]+ ion was generated in a straightforward two-electron oxidation reaction from mercury(II) dihydrazide and Ag[GaCl4]. Moreover, previous structure data of Me 3Si-Ni=N-SiMe3 were revised on the basis of new data. Cold, blue, and positive: The first homoleptic diazenium cation has been formed by treating mercury(II) dihydrazide with Ag[GaCl4] at low temperature. While numerous attempts at the direct silylation of diazene failed, this alternative new two-electron oxidation of the trisilylated hydrazide ion affords blue, highly labile [(Me3Si)2Ni=N-SiMe 3]+ ions in almost quantitative yield.
- Baumann, Wolfgang,Michalik, Dirk,Reiss, Fabian,Schulz, Axel,Villinger, Alexander
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Read Online
- Synthesis and characterization of redox active cyrhetrene-triazole click products
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We report the synthesis and characterization of two new cyclopentadienyl tricarbonyl rhenium(I) (cyrhetrene) complexes modified with a 1,4-disubstituted 1,2,3-triazole moiety. The two compounds, (η5-[4-phenyltriazol-1-yl]cyclopentadienyl) trica
- Day, David P.,Dann, Thomas,Blagg, Robin J.,Wildgoose, Gregory G.
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Read Online
- Synthesis and Reactivity of 5-Heterotruxenes Containing Sulfur or Nitrogen as the Heteroatom
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This paper presents an alternative path for the synthesis of 5-thiatruxene and the synthetic approach for 5-azatruxene not known so far. A new method for 5-thiatruxene improves the overall reaction yield from 17.5 to 22.6%, diminishes the synthesis time and costs by reducing synthetic steps from 5 to 2, and simplifies the isolation of intermediate and final products. The overall reaction yield for 5-azatruxene is 32.4%. The typical reactivity of both aromatic systems is also demonstrated. Recent research results suggest the use of 5-thiatruxene as the acceptor subunit of soluble blue emitters.
- Górski, Krzysztof,Mech-Piskorz, Justyna,Le?niewska, Barbara,Pietraszkiewicz, Oksana,Pietraszkiewicz, Marek
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- Copper(I)-Catalyzed Ketenimine Formation/Aza-Claisen Rearrangement Cascade for Stereoselective Synthesis of α-Allylic Amidines
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A copper-catalyzed three-component reaction of terminal alkynes, TsN3, and tertiary allylic amines is developed toward the one-pot synthesis of α-allylic amidines. The product was synthesized on gram scale under 1 mol % of catalyst loading. Transformations of products into alkenyl amine and other nitrogen-containing compounds are demonstrated without any loss of stereochemical information.
- Wang, Cheng-Gang,Wu, Rui,Li, Ting-Peng,Jia, Tao,Li, Yang,Fang, Dongmei,Chen, Xiaozhen,Gao, Yuanji,Ni, Hai-Liang,Hu, Ping,Wang, Bi-Qin,Cao, Peng
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Read Online
- Tandem Fragmentation of Cyclopropylcarbinyl/Oxiranylcarbinyl Radicals. On the Reversibility of Oxiranylcarbinyl/Allyloxyl Radical Formation
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The tandem radical fragmentation of four stereoisomeric epoxy thiocarbonates 7c-10c has been investigated.In each instance a cyclopropylcarbinyl radical fragments to generate an oxiranylcarbinyl radical, which, in turn, undergoes fragmentation.The initially detected product is (Z)-allylic alcohol 23, which isomerizes to (E)-allylic alcohol 24 under acid catalysis.The reversibility of allyloxyl radical formation is considered.
- Ziegler, Frederick,Petersen, Anders K.
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Read Online
- Powerful Direct C-H Amidation Polymerization Affords Single-Fluorophore-Based White-Light-Emitting Polysulfonamides by Fine-Tuning Hydrogen Bonds
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The development of white-light-emitting polymers has been actively pursued because of the importance of such polymers in various applications, such as lighting sources and displays. To generate white-light, numerous research efforts have focused on synthe
- Choi, Tae-Lim,Hwang, Soon-Hyeok,Kim, Hongsik,Lee, Dongwhan,Ryu, Hanseul,Serdiuk, Illia E.
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supporting information
p. 1778 - 1785
(2022/01/19)
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- Synthesis of Functionalized Silsesquioxane Nanomaterials by Rhodium-Catalyzed Carbene Insertion into Si?H Bonds
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We report carbene insertion into Si?H bonds of polyhedral oligomeric silsesquioxanes (POSS) for the synthesis of highly functionalized siloxane nanomaterials. Dirhodium(II) carboxylates catalyze insertion of aryl-diazoacetates as carbene precursors to afford POSS structures containing both ester and aryl groups as orthogonal functional handles for further derivatization of POSS materials. Four diverse and structurally varied silsesquioxane core scaffolds with one, three, or eight Si?H bonds were evaluated with diazo reactants to produce a total of 20 new POSS compounds. Novel diazo compounds containing a fluorinated octyl group and boron-dipyrromethene (BODIPY) chromophore demonstrate the use of highly functionalized substrates. Transformations of aryl(ester)-functionalized POSS compounds derived from this method are demonstrated, including ester hydrolysis and Suzuki–Miyaura cross-coupling.
- Franz, Annaliese K.,Jagannathan, Jake R.,Targos, Karina
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supporting information
(2021/11/27)
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- Ambruticins: tetrahydropyran ring formation and total synthesis
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The ambruticins are a family of polyketide natural products which exhibit potent antifungal activity. Gene knockout experiments are in accord with the proposal that the tetrahydropyran ring of the ambruticins is formedviathe AmbJ catalysed epoxidation of the unsaturated 3,5-dihydroxy acid, ambruticin J, followed by regioselective cyclisation to ambruticin F. Herein, a convergent approach to the total synthesis of ambruticin J is described as well as model studies involving epoxidation and cyclisations of unsaturated hydroxy esters to give tetrahydropyrans and tetrahydrofurans. The total synthesis involves preparation of three key fragments which were unitedviaa Suzuki-Miyaura cross-coupling and Julia-Kocienski olefination to generate the required carbon framework. Global deprotection to a triol and selective oxidation of the primary alcohol gave, after hydrolysis of the lactone, ambruticin J.
- Bowen, James I.,Crump, Matthew P.,Wang, Luoyi,Willis, Christine L.
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supporting information
p. 6210 - 6215
(2021/07/28)
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- Catalyst-free, scalable heterocyclic flow photocyclopropanation
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Industrial process development is driven by several factors, including safety, cost, robustness and environmental aspects. However, attempts to establish aryl diazo esters-which are highly valued in academic research for their reactivity as carbene precur
- Kl?pfer, Viktor,Eckl, Robert,Flo?, Johannes,Roth, Philippe M. C.,Reiser, Oliver,Barham, Joshua P.
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supporting information
p. 6366 - 6372
(2021/09/10)
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- Catalyst-free one-pot, four-component approach for the synthesis of di- And tri-substituted: N -sulfonyl formamidines
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A straightforward one-pot, multicomponent approach was developed to synthesize di- and tri-substituted N-sulfonyl formamidines from sulfonyl chlorides, NaN3, ethyl propiolate, and primary/secondary amines under mild conditions without catalysts or additives. Structural analysis of the di-substituted sulfonyl formamidines indicated formation of the E-syn/anti isomeric form. Tri-substituted analogues only formed E-isomers.
- Liu, Ai-Ran,Zhang, Lei,Li, Jiao,Wusiman, Abudureheman
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p. 15161 - 15166
(2021/05/19)
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- Development of prohibitin ligands against osteoporosis
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Current therapeutic approaches to osteoporosis display some potential adverse effects and a limited efficacy on non-vertebral fracture reduction. Some sulfonylamidines targeting the scaffold proteins prohibitins-1 and 2 (PHB1/2) have been showed to inhibit the formation of osteoclasts in charge of bone resorption. Herein, we report the development of a second generation of anti-osteoclastic PHB ligands. The most potent compound, IN45, showed 88% inhibition at the low concentration of 5 μM, indicates that it might serve as a basis for the development of new antiosteoporotic drugs.
- Tabti, Redouane,Lamoureux, Fran?ois,Charrier, Céline,Ory, Benjamin,Heymann, Dominique,Bentouhami, Embarek,Désaubry, Laurent
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supporting information
(2020/11/04)
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- Synthesis of 2-Prenylated Alkoxylated Benzopyrans by Horner-Wadsworth-Emmons Olefination with PPARα/γAgonist Activity
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We have synthesized series of 2-prenylated benzopyrans as analogues of the natural polycerasoidol, a dual PPARα/γagonist with anti-inflammatory effects. The prenylated side chain consists of five or nine carbons with an α-alkoxy-α,β-unsaturated ester moiety. Prenylation was introduced via the Grignard reaction, followed by Johnson-Claisen rearrangement, and the α-alkoxy-α,β-unsaturated ester moiety was introduced by the Horner-Wadsworth-Emmons reaction. Synthetic derivatives showed high efficacy to activate both hPPARα and hPPARγas dual PPARα/γagonists. These prenylated benzopyrans emerge as lead compounds potentially useful for preventing cardiometabolic diseases.
- Cabedo, Nuria,Cortes, Diego,Franck, Xavier,Hennuyer, Nathalie,Staels, Bart,Vila, Laura,Villarroel-Vicente, Carlos,Bernabeu, álvaro,Figadère, Bruno,García, Ainhoa,Marín, Paloma
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p. 1783 - 1786
(2021/10/29)
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- Scalable Synthesis of Functionalized Ferrocenyl Azides and Amines Enabled by Flow Chemistry
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A scalable access to functionalized ferrocenyl azides has been realized in flow. By halogen-lithium exchange of ferrocenyl halides and trapping with tosyl azide, a variety of functionalized ferrocenyl azides were obtained in high yields. To allow a scalable preparation of these potentially explosive compounds, a flow protocol was developed accelerating the reaction time to minutes and circumventing accumulation of potentially hazardous intermediates. The corresponding ferrocenyl amines were then prepared by a reliable reduction process.
- Boeser, Lisa,Christmann, Mathias,Hartmayer, Bence,Heretsch, Philipp,Kleoff, Merlin,Sarkar, Biprajit,Schwan, Johannes
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supporting information
(2020/02/04)
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- C-6 site modified NanoLuc type analogues and preparation method and application thereof
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The invention provides C-6 site modified NanoLuc type analogues and a preparation method and application thereof. The C-6 site modified NanoLuc type analogues have a structure as shown in a formula Iwhich is described in the specification. In the formula I, R1 is selected from a group consisting of a 4-fluorophenyl group, a 4-chlorphenyl group, a 4-bromophenyl group, a 3-fluoro-4-aminophenyl group, a thienyl group, a furyl group, a 5-methylfuryl group, a naphth-2-yl group, a benzofuryl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a 4-hydroxymethylphenyl group, a 4-methoxyphenylgroup and a 4-mercaptophenyl group. The analogues can be used as a bioluminescent substrate for researching protein-protein and protein-ligand interactions, monitoring protein stability and bioluminescence resonance energy transfer and the like. The invention provides application of the analogues to in-vitro, cellular and in-vivo distribution imaging under the action of NanoLuc luciferase in virtue of bioluminescence and application of the analogues as a report signal to detect the pharmacological action and toxic action of a drug at an enzyme level, a cellular level and an animal level in thepresence of NanoLuc luciferase.
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Paragraph 0087; 0090; 0091
(2020/05/30)
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- One-pot synthesis of sulfonyl-1H-1,2,3-triazolyl-thiomorpholine 1,1-dioxide derivatives and evaluation of their biological activity
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A one-pot procedure for the synthesis of novel 1,2,3-triazole derivatives (5a–5l) in good yields (63 to 77%) using different sulfonic acids and 4-(prop-2-yn-1-yl)thiomorpholine 1,1-dioxide through the in situ generated sulfonyl azides was developed. The structures of the newly synthesized compounds were confirmed by 1H NMR, 13C NMR, mass spectrometry, and elemental analysis. The newly synthesized compounds were screened for in?vitro antibacterial activity and free radical scavenging activity in terms of hydrogen donating or radical scavenging ability by the DPPH method. Among all, the compound N-(4-((4-((1,1-dioxidothiomorpholino) methyl)-1H-1,2,3-triazol-1-yl)sulfonyl)phenyl) acetamide (5l) was found to exhibit potent activity as compared to the standard drugs.
- Sreerama, Rakesh,Narasimha Swamy,Ravinder,Vasudeva Reddy,Narsimha, Sirassu
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p. 455 - 460
(2020/12/17)
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- Rh(III)-Catalyzed C(8)-H Activation of Quinoline N-Oxides: Regioselective C-Br and C-N Bond Formation
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A highly efficient and regioselective Rh(III)-catalyzed protocol for C8-bromination and amidation of quinoline N-oxide was developed. The transformation was found to be successful up to gram scale with excellent functional group tolerance and wide substrate scope. The mechanistic study revealed five-membered rhodacycle with quinoline N-oxide as a key intermediate for regioselective C8-functionalization. In addition, NFSI (N-fluorobis(phenylsulfonyl)-imide) was explored as an amidating reagent for C8-amidation of quinoline N-oxide for the first time.
- Dhiman, Ankit Kumar,Gupta, Shiv Shankar,Sharma, Ritika,Kumar, Rakesh,Sharma, Upendra
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p. 12871 - 12880
(2019/11/02)
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- Rh-catalyzed intramolecular cyclization of 1-sulfonyl-1,2,3-triazole and sulfinate. Concise preparation of sulfonylated unsaturated piperidines
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When 4-[3-(methanesulfinyloxy)propyl]-1-(arenesulfonyl)-1,2,3-triazoles were treated with rhodium catalysts of the type Rh2(RCO2)4, a new intramolecular cyclization took place to afford 2,3-didehydro-1-(arenesulfonyl)-3-(m
- Furukawa, Ayana,Hata, Takeshi,Shigeta, Masayuki,Urabe, Hirokazu
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supporting information
p. 815 - 819
(2019/02/25)
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- Asymmetric Synthesis and Chiroptical Properties of Enantiopure Helical Ferrocenes
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An enantiopure helical ferrocene (Rp)-5 with five ortho-condensed aromatic rings was synthesized using a PtCl2-catalyzed cycloisomerization of planar-chiral 2-ethynyl-1-(4-phenanthrenyl)ferrocene (Rp)-6f, prepared in 3 steps from known enantiopure sulfinyl ferrocenyl boronic acid (SS,Sp)-7, as the source of planar chirality. This pentacyclic helical ferrocene showed a very high optical rotation value and strong circular dichroism (CD) signals.
- Urbano, Antonio,Del Hoyo, Ana M.,Martínez-Carrión, Alicia,Carre?o, M. Carmen
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supporting information
p. 4623 - 4627
(2019/06/17)
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- Nitrene transfer catalyzed by a non-heme iron enzyme and enhanced by non-native small-molecule ligands
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Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that Pseudomonas savastanoi ethylene-forming enzyme, a non-heme iron enzyme, can catalyze olefin aziridination and nitrene C-H insertion, and that these activities can be improved by directed evolution. The non-heme iron center allows for facile modification of the primary coordination sphere by addition of metal-coordinating molecules, enabling control over enzyme activity and selectivity using small molecules.
- Goldberg, Nathaniel W.,Knight, Anders M.,Zhang, Ruijie K.,Arnold, Frances H.
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supporting information
p. 19585 - 19588
(2019/12/24)
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- A simple route towards the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles from primary amines and 1,3-dicarbonyl compounds under metal-free conditions
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An acetic acid-promoted approach that enables the synthesis of 1,4,5-trisubstituted 1,2,3-triazole derivatives has been achieved. This transformation employs readily available primary amines, 1,3-dicarbonyls and tosyl azide as the starting materials via a
- Guo, Ningxin,Liu, Xiufen,Xu, Hongyan,Zhou, Xi,Zhao, Huaiqing
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supporting information
p. 6148 - 6152
(2019/07/03)
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- Microchannel synthesis method of aryl sulfonyl azide
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The invention discloses a microchannel synthesis method of aryl sulfonyl azide. Sodium azide and water are uniformly stirred and prepared into a material A, aryl sulfonyl chloride and acetone are uniformly stirred and prepared into a material B, and the material A and the material B are continuously fed into a microchannel reactor at the flow rate of 6mL/min-70mL/min and efficiently react to prepare the aryl sulfonyl azide. Compared with the prior art, the microchannel synthesis method has the advantages that process route operation is safe, conversion rate is high, cost is saved, and the yield of the aryl sulfonyl azide is higher than 80%.
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Paragraph 0024-0029
(2019/07/04)
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- Spiro [cyclopropane-1,3-indoline] structural compound, crystal and preparation method and use thereof
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The invention discloses a spiro [cyclopropane-1,3-indoline] structural compound, a crystal and a preparation method and a use thereof. The structural formula of the compound is as shown in Formula I,the crystal form of the compound is a trigonal system, the unit cell parameters alpha is 73.580 (4) degree, beta is 83.539 (4)degree, gamma is 85.980 (4) degree, and the space group is P-1,Z=2, the cell volume is 1323.16(11)A. The invention also discloses a method for preparing the crystal form and the use of the compound of the invention, or a crystal form thereof, or a solvate thereof, or a pharmaceutically acceptable salt thereof, in the preparation of an antibacterial drug. The crystal form of the invention has high yield and purity, the crystal form of the compound with high purity iseasily obtained, the operation is simple and the cost is low, and the quality control of the compound represented by the formula (I) is greatly facilitated; at the same time, due to the hygroscopicityof the crystal form of the compound is not increased significantly, stability is good, a great convenience is provided for the late product transportation, storage or preparation process.
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Paragraph 0035; 0036
(2019/07/16)
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- A tetrahydropyran [2, 3 - b] indole skeleton object and its crystal and its preparation and use
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The invention discloses a tetrahydropyrane[2,3-b]indole framework material as well as a crystal, a preparation method and an application thereof. The framework material has the structural formula shown in formula I, the crystal form of the compound is a monoclinic system, the crystal cell parameters are shown as follows: a is 9.5716 (4) angstrom, b is 9.7736(3) angstrom, c is 9.6582(4) angstrom, alpha is 90 degrees, beta is 100.380(4) degrees, gamma is 90 degrees, the space group is P21, Z is 2, and the crystal cell volume is 888.74(6) angstrom. The invention also discloses the preparationmethod of the crystal form as well as an application of the compound or the crystal form, a solvate or pharmaceutically acceptable salt thereof in preparing antibacterial medicines. The yield and purity of the crystal form are high, the crystal form of the high-purity compound can be obtained easily, the operation is simple, the cost is low, and the quality control of the compound shown in formulaI is better facilitated. Meanwhile, the crystal form hygroscopicity of the compound is not obviously increased, the stability is good, and great convenience is brought to the later product transportation, storage or preparation process.
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Paragraph 0038-0040
(2019/11/20)
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- Caged cyclopropenes for controlling bioorthogonal reactivity
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Bioorthogonal ligations have been designed and optimized to provide new experimental avenues for understanding biological systems. Generally, these optimizations have focused on improving reaction rates and orthogonality to both biology and other members of the bioorthogonal reaction repertoire. Less well explored are reactions that permit control of bioorthogonal reactivity in space and time. Here we describe a strategy that enables modular control of the cyclopropene-tetrazine ligation. We developed 3-N-substituted spirocyclopropenes that are designed to be unreactive towards 1,2,4,5-tetrazines when bulky N-protecting groups sterically prohibit the tetrazine's approach, and reactive once the groups are removed. We describe the synthesis of 3-N spirocyclopropenes with an appended electron withdrawing group to promote stability. Modification of the cyclopropene 3-N with a bulky, light-cleavable caging group was effective at stifling its reaction with tetrazine, and the caged cyclopropene was resistant to reaction with biological nucleophiles. As expected, upon removal of the light-labile group, the 3-N cyclopropene reacted with tetrazine to form the expected ligation product both in solution and on a tetrazine-modified protein. This reactivity caging strategy leverages the popular carbamate protecting group linkage, enabling the use of diverse caging groups to tailor the reaction's activation modality for specific applications.
- Kumar, Pratik,Jiang, Ting,Li, Sining,Zainul, Omar,Laughlin, Scott T.
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supporting information
p. 4081 - 4085
(2018/06/12)
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- Regioselective: Ortho -functionalization of bromofluorenecarbaldehydes using TMPMgCl·LiCl
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A highly regioselective functionalization of 7-bromofluorene-2-carbaldehydes, potent organic chromophores, in position C3 using a mild ortho-metallation strategy (DoM) with TMPMgCl·LiCl has been developed. This approach allows the preparation of highly functionalized fluorene derivatives by conversion of the in situ generated metalated species with various electrophiles giving a fast access to novel organic phosphorescent dyes.
- G?bel, Dominik,Clamor, Nils,Nachtsheim, Boris J.
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supporting information
p. 4071 - 4075
(2018/06/12)
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- Chlorobenzene-pyridine compounds and application thereof
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The invention relates to chlorobenzene-pyridine compounds and an application thereof. The compounds can be used for preparing a Smoothened protein inhibitor and a drug for resisting adenocarcinoma andesophagus cancer and have the structure in the general formula (I) shown in the description, wherein X is selected from the structure shown in the description, R1 is selected from H or the structureshown in the description, and R2 is selected from the structure shown in the description.
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Paragraph 0051;
(2018/04/01)
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- Indole and dihydro pyridine compound and its crystalline form and preparation method (by machine translation)
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The present invention provides a compound of formula (A) illustrated compound and its preparation method. The invention also provides formula (A) shown in crystalline form of compound I, the crystalline form is a rhombohedral crystal system, space group is P31 , Unit cell parameters a=14.0995 (7) Α=90°, b=14.0995 (7) Β=90°, c=11.2241 (5) Γ=120°, Z=3, cell volume=1932.4 (2) The invention also provides a method for preparing the crystalline form I of. The present invention successfully to obtain the indole and dihydro pyridine compound and its crystalline form, and the compounds of the invention or its crystalline form has certain antibacterial activity, and the moisture increase is not obvious, stability is good, the late the product transportation, storage or preparation process provides great convenience. (by machine translation)
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Paragraph 0027; 0028
(2018/05/01)
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- Tert -Butyl nitrite mediated nitrogen transfer reactions: Synthesis of benzotriazoles and azides at room temperature
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A conversion of o-phenylenediamines into benzotriazoles was achieved at room temperature using tert-butyl nitrite. The optimized conditions are also well suited for the transformation of sulfonyl and acyl hydrazines into corresponding azides. This protocol does not require any catalyst or acidic medium. The desired products were obtained in excellent yields in a short span of time.
- Azeez, Sadaf,Chaudhary, Priyanka,Sureshbabu, Popuri,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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supporting information
p. 6902 - 6907
(2018/10/02)
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- New oligodeoxyribonucleotide derivatives bearing internucleotide N-tosyl phosphoramidate groups: Synthesis and complementary binding to DNA and RNA
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N-Sulfonyl phosphoramidate derivatives of oligodeoxyribonucleotides containing N-tosyl phosphoramidate groups are first reported. The synthesis is based on Staudinger reaction between tosyl azide and 3′,5′-dinucleoside β-cyanoethyl phosphite comprising the immobilized oligonucleotide, which is obtained by the phosphoramidite coupling during the solid-phase oligonucleotide synthesis. The N-tosyl phosphoramidate group was stable under conditions of the oligonucleotide synthesis, in particular, upon acidic detritylation followed by the removal of protective groups and cleavage from the polymer support by the treatment with concentrated aqueous ammonia at 55°C. The stability of DNA and RNA duplexes of the model oligonucleotides containing N-tosyl phosphoramidate groups was only slightly lower than that of native DNA:DNA and DNA:RNA duplexes, respectively.
- Prokhorova,Chelobanov,Burakova,Fokina,Stetsenko
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- Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si-H and S-H Bonds
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An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds was developed. A wide range of α-silylesters and α-thioesters was obtained in high yields (up to 98%) from α-diazoesters using 5 mol% of a simple copper(I) salt as catalyst. Using 0.05 mol% of the same catalyst, α-diazoketones led to α-silylketones in low to good yields (up to 70%).
- Keipour, Hoda,Jalba, Angela,Delage-Laurin, Léo,Ollevier, Thierry
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p. 3000 - 3010
(2017/03/23)
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- Iron-Catalyzed Carbene Insertion Reactions of α-Diazoesters into Si-H Bonds
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An efficient iron-catalyzed carbene insertion reaction of α-diazo carbonyl compounds into the Si-H bond was developed. A wide range of α-silylesters was obtained in high yields (up to 99%) from α-diazoesters using a simple iron(II) salt as catalyst.
- Keipour, Hoda,Ollevier, Thierry
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supporting information
p. 5736 - 5739
(2017/11/10)
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- A new way to do an old reaction: highly efficient reduction of organic azides by sodium iodide in the presence of acidic ion exchange resin
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Organic azides are readily reduced to the corresponding amines by treatment with sodium iodide in the presence of acidic ion exchange resin. The process, optimal when performed at 40 °C and 200 mbar pressure on a rotatory evaporator, is extremely efficient, clean, and tolerant of a variety of functional groups.
- Suthagar, Kajitha,Fairbanks, Antony J.
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supporting information
p. 713 - 715
(2017/01/13)
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- Taming tosyl azide: The development of a scalable continuous diazo transfer process
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Heat and shock sensitive tosyl azide was generated and used on demand in a telescoped diazo transfer process. Small quantities of tosyl azide were accessed in a 'one pot' batch procedure using shelf stable, readily available reagents. For large scale diaz
- Deadman, Benjamin J.,O'Mahony, Rosella M.,Lynch, Denis,Crowley, Daniel C.,Collins, Stuart G.,Maguire, Anita R.
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supporting information
p. 3423 - 3431
(2016/04/09)
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- Synthesis and cytotoxicity evaluation of aryl triazolic derivatives and their hydroxymethine homologues against B16 melanoma cell line
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In this manuscript we describe synthesis and cytotoxicity evaluation of some triazolic derivatives against B16 melanoma cell line. For this purpose, we transformed a set of aromatic aldehydes into terminal alkynes, using Besthmann-Ohira reagent, and we made the corresponding hydroxymethyl homologated alkynes by an acetylene Grignard reagent. These generated two sets of alkynes were then subjected to a copper(I)-catalyzed alkyne-azide cycloaddition reaction (CuAAC) using a solid-supported catalyst (Amberlyst A-21?CuI), with a third set composed of organic azides. Synthesized triazoles were then tested in?vitro against B16 melanoma cell line. Amongst them, compounds a1b1 (R1?=?p-nitrophenyl, R2?=?benzyl), a4b1 (R1?=?naphthyl, R2?=?benzyl) and a4b5 (R1?=?naphthyl, R2?=?(R/S)- dioxolane) showed the best activity against B16 melanoma cells, with IC50of 5.12, 3.89 and 6.60?μM respectively.
- Kalhor-Monfared, Shiva,Beauvineau, Claire,Scherman, Daniel,Girard, Christian
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supporting information
p. 436 - 441
(2016/07/15)
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- DABCO/AcOH Jointly Accelerated Copper(I)-Catalysed Cycloaddition of Azides and Alkynes on Water at Room Temperature
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An expeditious room temperature protocol for the synthesis of 1,4-disubstituted 1,2,3-triazoles from terminal alkynes and substituted azides has been achieved using the combination of CuSO4-ascorbate/1,4-diazabicyclo[2.2.2]octane/acetic acid. This expeditious protocol is applicable to aryl, alkyl, and sulfonyl azides. Acetic acid accelerates the protonation of cuprated triazole and thus avoids the possible side reactions. Devoid of acetic acid, the reaction pathway alters to the ketinimine route and results in the formation of sulfonamides.
- Sarode, Prashant B.,Bahekar, Sandeep P.,Chandak, Hemant S.
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supporting information
p. 2681 - 2684
(2016/11/26)
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- As cell necrosis inhibitors of the indole compounds (by machine translation)
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The invention relates to chemical formula (1) indole compounds, or its pharmaceutically acceptable salt or isomer, and in containing the same as the characteristic, as an active ingredient for the prevention or treatment of cell necrosis and its associated disease composition and method of manufacturing. (by machine translation)
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Paragraph 0222
(2016/10/09)
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- Synthesis of Sulfonyl Azides via Lewis Base Activation of Sulfonyl Fluorides and Trimethylsilyl Azide
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A protocol for the efficient conversion of sulfonyl fluorides into sulfonyl azides through Lewis base activation is described. The in situ generated sulfonyl azides are efficient diazo-transfer agents, affording diazo compounds and primary azides in excellent yields.
- Barrow, Andrew S.,Moses, John E.
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supporting information
p. 1840 - 1843
(2016/07/16)
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- Highly efficient reduction of carbonyls, azides, and benzyl halides by NaBH4 in water catalyzed by PANF-immobilized quaternary ammonium salts
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A series of polyacrylonitrile fiber-supported quaternary ammonium salts (PANF-QAS) were prepared and applied to the catalytic reduction of aldehydes, ketones, azides, and benzyl halides in water using NaBH4 as the reducing reagent in a highly efficient, economic, and environmentally benign way. The structure-activity relationships were investigated, which showed that the catalysts made up of quaternary ammonium salts with longer alkyl chains, larger cationic radii and better lipophilicity speed up the reduction reaction to afford the products in excellent yield. Moreover, the optimized catalyst can be applied to the reduction of 1-naphthaldehyde in a continuous flow process with outstanding reactivity and recyclability.
- Du, Jianguo,Xu, Gang,Lin, Huikun,Wang, Guangwei,Tao, Minli,Zhang, Wenqin
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supporting information
p. 2726 - 2735
(2016/05/24)
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- Synthesis of diversely functionalised 2,2-disubstituted oxetanes: Fragment motifs in new chemical space
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Di-, tri- and tetra-substituted oxetane derivatives with combinations of ester, amide, nitrile, aryl, sulfone and phosphonate substituents are prepared as fragments or building blocks for drug discovery. The synthesis of these novel oxetane functional groups, in new chemical space, is achieved via rhodium-catalysed O-H insertion and C-C bond forming cyclisation.
- Davis, Owen A.,Croft, Rosemary A.,Bull, James A.
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supporting information
p. 15446 - 15449
(2015/10/20)
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- Nucleophilic Substitution Reactions of 2,4-Dinitrophenyl X-Substituted-Benzenesulfonates and Y-Substituted-Phenyl 4-Nitrobenzenesulfonates with Azide Ion: Regioselectivity and Reaction Mechanism
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The second-order rate constants for reactions of 2,4-dinitrophenyl X-substituted-benzenesulfonates (4a-4f) and Y-substituted-phenyl-4-nitrobenzenesulfonates (5a-5f) with N3- ion have been measured spectrophotometrically. The reactions of 4a-4f proceed through S-O and C-O bond fission pathways competitively. Fraction of the S-O bond fission decreases rapidly as the substituent X in the benzenesulfonyl moiety changes from an electron-withdrawing group to an electron-donating group. The Hammett plots for reactions of 4a-4f are linear with ρX=1.87 and 0.56 for the S-O and C-O bond fission, respectively. The fact that the substituent X is further away from the reaction site of the C-O bond fission than that of the S-O bond fission is one reason for the smaller ρX value. The nature of the reaction mechanism (i.e., a stepwise mechanism in which expulsion of the leaving group occurs after the rate-determining step) is also responsible for the smaller ρX value obtained from the C-O bond fission. The Bronsted-type plot for the reactions of 5a-5f is linear with βlg=-0.63, which is typical for reactions reported previously to proceed through a concerted mechanism. Effects of substituents X and Y on regioselectivity and reaction mechanism are discussed in detail.
- Moon, Ji-Hyun,Kim, Min-Young,Han, So-Yeop,Um, Ik-Hwan
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p. 1360 - 1365
(2015/07/15)
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- Synthesis of 1,2,3-triazoles from azide-derivatised aminocyclitols by catalytic diazo transfer and CuAAC click chemistry
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CuII-catalysed diazo transfer and CuI-catalysed azide-alkyne 1,3-dipolar cycloaddition (CuAAC) "click chemistry" were used to synthesis C7N aminocyclitol-derivatised 1,2,3-triazoles. In the course of this work, the -N=N- moiety was transferred onto C7N aminocyclitols such as validamine, valienamine and valiolamine by employing imidazole-1-sulfonyl azide as the diazo transfer reagent with catalysis by CuII, ZnII and NiII, in moderate to good yields. The obtained azidocyclitols were coupled with various terminal alkynes under modified Meldal's conditions with good to excellent yields. The stereo- and regiochemistry of the products were confirmed by 2D-NMR (NOESY and HMBC). One-pot syntheses of the corresponding 1,2,3-triazoles, as safer and more efficient procedures, were also investigated and gave moderate to good yields. Copyright
- Ji, Li,Zhou, Guo-Quan,Qian, Chao,Chen, Xin-Zhi
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supporting information
p. 3622 - 3636
(2014/06/23)
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- IMIDAZOPYRIDINE COMPOUNDS AND USES THEREOF
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This invention generally relates to substituted imidazopyridine compounds, particularly substituted 4-(imidazo[1,2-a]pyridin-2-yl)benzamide compounds and salts thereof. This invention also relates to pharmaceutical compositions and kits comprising such a compound, uses of such a compound (including, for example, treatment methods and medicament preparations), processes for making such a compound, and intermediates used in such processes.
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Paragraph 216
(2014/08/19)
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- Synthesis and antiviral evaluation of 4′-(1,2,3-triazol-1-yl) thymidines
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Non-obligate chain terminating nucleosides with a linear substituent (azido or ethynyl group) at the 4′ position represent an important class of compounds in antiviral discovery, particularly against hepatitis C virus (HCV) and human immunodeficiency virus (HIV). We have previously shown that 3′-azidothymidine (AZT)-derived 1,2,3-triazoles can be potent inhibitors of HIV-1. To gauge the medicinal chemistry impact of functionalizing the 4′-linear substituent and possibly generate novel antiviral nucleoside scaffolds, we have explored azide-alkyne cycloaddition reactions with 4′-azidothymidine (ADRT). The Ru-mediated reaction failed and the Cu-catalyzed variant generated 1,2,3-triazoles (9a-y) with only modest yields and efficiencies, indicating a substantial steric barrier around the 4′-azido group. Antiviral screening identified a few triazole analogues moderately active against HIV-1 (18-62% inhibition at 10 μM) and/or influenza A virus (15-50% inhibition at 10 μM), and none active against West Nile virus (WNV) or HCV. These results suggest that the linear 4′ azido group of ADRT may be essential for target binding and that its chemical manipulation could largely compromise antiviral potency. This journal is the Partner Organisations 2014.
- Vernekar, Sanjeev Kumar V.,Qiu, Li,Zacharias, Jeana,Geraghty, Robert J.,Wang, Zhengqiang
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supporting information
p. 603 - 608
(2014/05/06)
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- Zinc chloride catalyzed ring opening of N-arylsulfonyl aziridines by thioamides: A new approach to the synthesis of amidines
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The first zinc chloride catalyzed ring opening of N-arylsulfonyl aziridines by thioamides is described. Various thioamides were reacted with N-arylsulfonyl aziridines in the presence of a catalytic amount of dry zinc chloride to provide the corresponding
- Hajibabaei, Khadijeh,Zali-Boeini, Hassan
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supporting information
p. 2044 - 2048
(2014/11/08)
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- 2'-AZIDO SUBSTITUTED NUCLEOSIDE DERIVATIVES AND METHODS OF USE THEREOF FOR THE TREATMENT OF VIRAL DISEASES
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The present invention relates to 2′-Azido Substituted Nucleoside Derivatives of Formula (I): and pharmaceutically acceptable salts thereof, wherein B, X, R1, R2 and R3 are as defined herein. The present invention also relates to compositions comprising at least one 2′-Azido Substituted Nucleoside Derivative, and methods of using the 2′-Azido Substituted Nucleoside Derivatives for treating or preventing HCV infection in a patient.
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Paragraph 0230; 0231
(2014/08/06)
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- Synthesis of 1,2-amino alcohols via catalytic C-H amidation of sp3 methyl C-H bonds
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Herein a new synthetic route to 1,2-amino alcohols is presented by using C-H amidation of sp3 methyl C-H bonds as a key step. Readily available alcohols were employed as starting materials after converting them to removable ketoxime chelating g
- Kang, Taek,Kim, Heejeong,Kim, Jeung Gon,Chang, Sukbok
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supporting information
p. 12073 - 12075
(2014/12/11)
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- Synthesis of sulfonyl azides via diazotransfer using an imidazole-1-sulfonyl azide salt: Scope and 15N NMR labeling experiments
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Imidazole-1-sulfonyl azide hydrogen sulfate is presented as an efficient reagent for the synthesis of sulfonyl azides from primary sulfonamides. The described method is experimentally simple and high-yielding and does not require the addition of Cu salts. Furthermore, 15N NMR mechanistic studies show the reaction proceeds via a diazo transfer mechanism. Imidazole-1-sulfonyl azide hydrogen sulfate provides a considerable advantage over existing diazo transfer reagents in terms of impact stability, cost, and ease of use.
- Stevens, Marc Y.,Sawant, Rajiv T.,Odell, Luke R.
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p. 4826 - 4831
(2014/06/23)
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- Direct synthesis of sulfonyl azides from sulfonic acids
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A one-pot process for the synthesis of various sulfonyl azides (RSO2N3) by treating sulfonic acids with triphenylphosphine/trichloroisocyanuric acid/sodium azide at room temperature is described. A wide range of arenesulfonyl and alkanesulfonyl azides was obtained in excellent yields under mild conditions.
- Kiani, Adeleh,Akhlaghinia, Batool,Rouhi-Saadabad, Hamed,Bakavoli, Mehdi
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p. 119 - 127
(2014/01/23)
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- Clicking 3′-azidothymidine into novel potent inhibitors of human immunodeficiency virus
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3′-Azidothymidine (AZT) was the first approved antiviral for the treatment of human immunodeficiency virus (HIV). Reported efforts in clicking the 3′-azido group of AZT have not yielded 1,2,3-triazoles active against HIV or any other viruses. We report herein the first AZT-derived 1,2,3-triazoles with submicromolar potencies against HIV-1. The observed antiviral activities from the cytopathic effect (CPE) based assay were confirmed through a single replication cycle assay. Structure-activity-relationship (SAR) studies revealed two structural features key to antiviral activity: a bulky aromatic ring and the 1,5-substitution pattern on the triazole. Biochemical analysis of the corresponding triphosphates showed lower ATP-mediated nucleotide excision efficiency compared to AZT, which along with molecular modeling suggests a mechanism of preferred translocation of triazoles into the P-site of HIV reverse transcriptase (RT). This mechanism is corroborated with the observed reduction of fold resistance of the triazole analogue to an AZT-resistant HIV variant (9-fold compared to 56-fold with AZT).
- Sirivolu, Venkata Ramana,Vernekar, Sanjeev Kumar V.,Ilina, Tatiana,Myshakina, Nataliya S.,Parniak, Michael A.,Wang, Zhengqiang
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supporting information
p. 8765 - 8780
(2013/12/04)
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- Photoassisted synthesis of enantiopure alkaloid mimics possessing unprecedented polyheterocyclic cores
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Enantiopure alkaloid mimics are synthesized via high yielding intramolecular cycloadditions of photogenerated azaxylylenes tethered to pyrroles, with further growth of molecular complexity via post-photochemical transformations of primary photoproducts. This expeditious access to structurally unprecedented polyheterocyclic cores is being developed in the context of diversity-oriented synthesis, as the modular design allows for rapid "pre-assembly" of diverse photoprecursors from simple building blocks/diversity inputs.
- Kumar, N.N. Bhuvan,Mukhina, Olga A.,Kutateladze, Andrei G.
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supporting information
p. 9608 - 9611
(2013/07/26)
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- β-diketiminato nickel imides in catalytic nitrene transfer to isocyanides
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The β-diketiminato nickel(I) species [Me3NN]Ni(2-picoline) (1) serves as an efficient catalyst for carbodiimide (RN=C=NR′) formation in the reactions of a range of organoazides N3R with isocyanides R′NC. [Me3NN]Ni(CNR)2 (R = tBu, Ar (Ar = 2,6-Me2C6H3)) species provide carbodiimides RN=C=NAr′ upon reaction with Ar′N3 (Ar′ = 3,5-Me2C6H3). Nitrene transfer takes place via the intermediacy of nickel imides. Reaction of [MexNN]Ni(2-picoline) (x = 2 or 3) with Ar′N3 gives the new dinickel imides {[Me xNN]Ni}2(μ-NAr′) (4 (x = 3) and 5 (x = 2)) as deep purple, diamagnetic substances. The X-ray structure of {[Me 2NN]Ni}2(μ-NAr′) (5) features short Ni-N imide distances of 1.747(2) and 1.755(2) A along with a short Ni-Ni distance of 2.7210(3) A. These dinickel imides 4 and 5 react stoichiometrically with tBuNC to provide the corresponding carbodiimides tBuN=C=NAr′ in good yield. Azide transfer takes place upon reaction of 1 with TMS-N3 to give the square planar nickel(II) azide [Me3NN]Ni(N3)(2-picoline) (7). Stoichiometric reaction of dinickel dicarbonyl {[Me3NN]Ni} 2(μ-CO)2 with organoazides such as Ar′N 3 is sluggish, indicating that 1 is not an efficient catalyst for nitrene transfer from organoazides to CO to form isocyanates RN=C=O.
- Wiese, Stefan,Aguila, Mae Joanne B.,Kogut, Elzbieta,Warren, Timothy H.
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supporting information
p. 2300 - 2308
(2013/06/27)
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