- Synthesis of the Bestmann-Ohira reagent
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The conversion of an aldehyde to a terminal alkyne by means of a one-carbon chain extension is a key reaction in organic synthesis. By using dimethyl 1-diazo-2-oxopropylphosphonate, the Bestmann-Ohira reagent, the transformation can be achieved in one pot. A reliable, convenient sequence for the preparation of the Bestmann-Ohira reagent is described. Georg Thieme Verlag Stuttgart.
- Pietruszka, Joerg,Witt, Andreas
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Read Online
- Insertion reaction of azidosulfonyl azo dye with model alicyclic and heterocyclic compounds
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Thermal reactions of 4-(2-hydroxynaphthalen-1-yldiazenyl)benzenesulfonyl azide with cyclohexane, benzene, toluene, anisole, p-xylene, mesitylene, dihydropyran, and pyridine were studied. Structures of the resulting azo dyes were confirmed by FT-IR, UV, 1H and 13C NMR, and mass spectra and elemental analyses, and their solvatochromic properties were examined. Probable mechanisms of nitrene insertion were discussed.
- Dabbagh,Teimouri
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Read Online
- Au-Cavitands: Size governed arene-alkyne cycloisomerization
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With an inwardly directed reactive center and a well-defined binding pocket, Au(I) functionalized resorcin[4]arene cavitands have been shown to catalyze molecular transformations. The reactivity profiles that emerge differ from other Au(I) catalysts. The added constraint of a binding pocket gives rise to the possibility that the substrates might have to fit into the resorcinarene pocket; our hypothesis is that substrates that match the available space have different reaction outcomes than those that do not. Herein we report on the intramolecular cyclization of alkyne-aromatic substrates with variable alkynes and aromatic composition. We see that scaffold size most drastically dictates reactivity, especially when the substrate's features are particularly designed. The results of these experiments add to the veritable goldmine of information about the selectivity in catalysis that cavitands offer.
- Rusali, Lisa E.,Schramm, Michael P.
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supporting information
(2020/09/15)
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- Synthesis of Allylboranes via Cu(I)-Catalyzed B-H Insertion of Vinyldiazoacetates into Phosphine-Borane Adducts
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Cu(I) catalysts enable C-B bond formation via direct insertion of vinyldiazoacetates into B-H bonds of borane-phosphine Lewis adducts to form phosphine-protected allylboranes under mild conditions. The resulting allylborane-phosphine Lewis adducts can be used in the diastereoselective allylation of aldehydes directly without the need for removal of the phosphine. The allylation reaction proceeds with high diastereoselectivity and yields 5,6-disubstituted dihydropyranones after treatment with an appropriate acid.
- Drikermann, Denis,M??el, Robert S.,Al-Jammal, Walid K.,Vilotijevic, Ivan
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supporting information
p. 1091 - 1095
(2020/02/15)
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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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- 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 0033-0034
(2019/07/04)
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- Visible-Light-Mediated Sulfonylimination of Tertiary Amines with Sulfonylazides Involving Csp3-Csp3 Bond Cleavage
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Visible-light-induced cross-coupling of arylsulfonyl azides with tertiaryamines in the presence of Eosin Y at room temperature has been achieved. This transformation features alkyl C-C bond cleavage and provides a green approach to N-sulfonylamidines under mild conditions.
- Gui, Jiao,Xie, Haisheng,Jiang, Huanfeng,Zeng, Wei
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supporting information
p. 2804 - 2807
(2019/04/30)
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- Palladium(0)-Catalyzed Carbonylative Synthesis of N-Acylsulfonamides via Regioselective Acylation
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N-Acylsulfonamides represent an important bioisostere of carboxylic acids that allow for greater molecular elaboration and enhanced hydrogen bonding capabilities. Herein, we present a mild and convenient palladium(0)-catalyzed synthesis of N-acylsulfonamides via the carbonylative coupling of sulfonyl azides and electron-rich heterocycles. The reaction proceeds via in situ generation of a sulfonyl isocyanate followed by regioselective acylation of an indole or pyrrole nucleophile. This approach has been used to synthesize 34 indole- and pyrrole-substituted N-acylsulfonamides in yields of up to 95%. Importantly, this process is ligand-free and compatible with an ex situ solid CO source and requires only slightly elevated temperatures, making it a highly attractive method for the preparation of this important class of compounds. This study further investigated the possibility of labeling N-acylsulfonamides with carbon-11 to facilitate biological evaluation and in vivo studies with positron emission tomography.
- Schembri, Luke S.,Eriksson, Jonas,Odell, Luke R.
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p. 6970 - 6981
(2019/06/14)
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- Ligand-Free, Quinoline N-Assisted Copper-Catalyzed Nitrene Transfer Reaction to Synthesize 8-Quinolylsulfimides
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An efficient copper-catalyzed, quinolyl N-directed nitrene transfer reaction to 8-quinolylsulfides was described. A variety of 8-quinolylsulfimides with different functional groups were synthesized in moderate to high yields. The obtained 8-quinolylsulfimides were proved to be promising novel type of bidentate ligands in Pd(II)-catalyzed allylic alkylation.
- Xiao, Xinsheng,Huang, Sanping,Tang, Shanshan,Jia, Guokai,Ou, Guangchuan,Li, Yangyan
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p. 7618 - 7629
(2019/06/27)
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- Photoinduced Cascade Reaction of Tertiary Amines with Sulfonyl Azides: Synthesis of Amidine Derivatives
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A metal-free cascade reaction of tertiary amines with sulfonyl azides promoted by acridinium salts under blue light irradiation was developed and provided amidine derivatives in moderate to good yields. Enamine was generated from tertiary amine via single-electron transfer promoted by acridinium salts, and the following [3+2] cyclization with sulfonyl azide and CH2N2 release afforded the desired products. (Figure presented.).
- Ding, Rui,Chen, Hui,Xu, Yan-Li,Tang, Hai-Tao,Chen, Yan-Yan,Pan, Ying-Ming
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supporting information
p. 3656 - 3660
(2019/07/10)
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- Water/Alkali-Catalyzed Reactions of Azides with 2-Cyanothioacetamides. Eco-Friendly Synthesis of Monocyclic and Bicyclic 1,2,3-Thiadiazole-4-carbimidamides and 5-Amino-1,2,3-triazole-4-carbothioamides
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The reactions of thioamides with azides in water were studied. It was reliably shown that the reaction of 2-cyanothioacetamides 1 with various types of azides 2 in water in the presence of alkali presents an efficient, general, one-step, atom-economic, and eco-friendly method for the synthesis of 1,2,3-thiadiazol-4-carbimidamides 5 and 1,2,3-triazole-4-carbothioamides 4. This method can be extended to the one-pot reaction of sulfonyl chlorides and 6-chloropyrimidines 2′o with sodium azide, leading to final products in higher yields, that is, avoiding the isolation of unsafe sulfonyl azides. The method was furthermore applied to the reaction of N,N′-bis-(2-cyanothiocarbonyl)pyrazine 1h with sulfonyl azides to afford bicyclic 1,2,3-thiadiazoles 8 and 1,2,3-triazoles 9 connected via a 1,1′-piperazinyl linker. 2-Cyanothioacetamides 1 were also shown to react with aromatic azides in water in the presence of alkali to afford 1-aryl-5-amino-1,2,3-triazole-4-carbothioamides 11. In contrast to aromatic azides and similarly to sulfonyl azides, 6-azidopyrimidine-2,4-diones 2o-q react with cyanothioacetamides to form N-pyrimidin-6-yl-5-dialkylamino-1,2,3-thiadiazole-4-N-l-carbimidamides 12. A mechanism was proposed to rationalize the role of water in changing the reactivity of azides toward 2-cyanothioacetamides.
- Filimonov, Valeriy O.,Dianova, Lidia N.,Beryozkina, Tetyana V.,Mazur, Dmitrii,Beliaev, Nikolai A.,Volkova, Natalia N.,Ilkin, Vladimir G.,Dehaen, Wim,Lebedev, Albert T.,Bakulev, Vasiliy A.
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p. 13430 - 13446
(2019/10/16)
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- Manganese-Catalyzed C?H Amidation of Heteroarenes in Water
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We have developed an efficient manganese-catalyzed amidation of various heteroarenes via C?H bond activation using readily available sulfonyl azides. The key step is heteroarene directed electrophilic aromatic metalation using MnBr(CO)5 as catalyst. This method offers excellent chemical yields and regioselectivity with good functional group tolerance. This base metal catalyzed reaction proceeds efficiently using water as the only solvent and nitrogen is the only byproduct. (Figure presented.).
- Kong, Xianqiang,Lin, Long,Xu, Bo
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supporting information
p. 2801 - 2805
(2018/08/17)
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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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- Cobalt(II)-Catalyzed Isocyanide Insertion Reaction with Sulfonyl Azides in Alcohols: Synthesis of Sulfonyl Isoureas
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A Co(II)-catalyzed isocyanide insertion reaction with sulfonyl azides in alcohols to form sulfonyl isoureas via nitrene intermediate has been developed. This protocol provides a new, environmentally friendly, and simple strategy for the synthesis of sulfonyl isourea derivatives by employing a range of substrates under mild conditions.
- Jiang, Tian,Gu, Zheng-Yang,Yin, Ling,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 7913 - 7919
(2017/08/14)
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- Product-Derived Bimetallic Palladium Complex Catalyzes Direct Carbonylation of Sulfonylazides
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A novel product-derived bimetallic palladium complex catalyzes a sulfonylazide-transfer reaction with the σ-donor/π-acceptor ligand CO, and is advantageous given its broad substrate scope, high efficiency, and mild reaction conditions (atmospheric pressure of CO at room temperature). This methodology provides a new approach to sulfonylureas, which are present in both pharmaceuticals and agrochemicals. The synthesis of Glibenclamide on a gram scale further revealed the practical utility of this procedure. Mechanistically, the generation of a bridged bimetallic palladium species derived from the product sulfonylurea is disclosed as the crucial step for this catalytic cycle.
- Zhao, Jin,Li, Zongyang,Song, Shaole,Wang, Ming-An,Fu, Bin,Zhang, Zhenhua
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supporting information
p. 5545 - 5549
(2016/05/09)
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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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- Semi-synthesis of biologically active nisin hybrids composed of the native lanthionine ABC-fragment and a cross-stapled synthetic DE-fragment
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The antimicrobial peptide nisin is a promising template for designing novel peptide-based antibiotics to improve its drug-like properties. First steps in that direction represent the synthesis of hybrid nisin derivatives that contain a native nisin ABC-part and synthesized cross-stapled DE-ring fragments and are described here. The biological activity of the newly synthesized nisin derivatives was evaluated in order to compare the bioactivity of the synthetic DE-ring containing mimic and native lanthionine-bridged DE-ring containing nisin. The native nisin ABC-ring system was obtained via chymotrypsin digestion of full-length nisin, and was subsequently functionalized at the C-terminal carboxylate with two different amino alkyne moieties. Next, nisin hybrids were successfully prepared using Cu(I)-catalyzed azide alkyne cycloaddition 'click' chemistry by chemo-selective ligation of the ABC-alkyne with the N-terminal azido functionalized dicarba-DE ring mimic. The newly synthesized compounds were active as potent lipid II binders and retained antimicrobial activity in a growth inhibition assay. However, pore formation was not observed, possibly either due to the different character of the 'staples' as compared to the parent sulfides, or due to the triazole moiety as a sub-optimal amide bond isostere.
- Slootweg, Jack C.,Peters, Nienke,Quarles Van Ufford,Breukink, Eefjan,Liskamp, Rob M.J.,Rijkers, Dirk T.S.
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supporting information
p. 5345 - 5353
(2014/12/11)
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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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- Cu-catalyzed multicomponent polymerization to synthesize a library of poly(N -sulfonylamidines)
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We report a versatile Cu-catalyzed multicomponent polymerization (MCP) technique that enables the synthesis of high-molecular-weight, defect-free poly(N-sulfonylamidines) from monomers of diynes, sulfonyl azides, and diamines. Through a series of optimizations, we discovered that the addition of excess triethylamine and the use of N,N′-dimethylformamide as a solvent are key factors to ensure efficient MCP. Formation of cyclic polyamidines was a side reaction during polymerization, but it was readily controlled by using diynes or diamines with long or rigid moieties. In addition, this polymerization is highly selective for three-component reactions over click reactions. The combination of the above factors enables the synthesis of high-molecular-weight polymers, which was challenging in previous MCPs. All three kinds of monomers (diynes, sulfonyl azides, and diamines) are readily accessible and stable under the reaction conditions, with various monomers undergoing successful polymerization regardless of their steric and electronic properties. Thus, we synthesized various high-molecular-weight, defect-free polyamidines from a broad range of monomers while overcoming the limitations of previous MCPs, such as low conversion and defects in the polymer structures.
- Lee, In-Hwan,Kim, Hyunseok,Choi, Tae-Lim
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supporting information
p. 3760 - 3763
(2013/04/24)
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- ACYLSULFONAMIDES AND PROCESSES FOR PRODUCING THE SAME
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The present disclosure relates to acylsulfonamides and processes for their preparation. The processes involve a target-guided synthesis approach, whereby a thioacid and a sulfonyl azide are reacted in the presence of a biological target protein, a Bcl-2 family protein, to form the acylsulfonamide.
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Page/Page column 93
(2012/03/09)
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- PYRIMIDYL CYCLOPENTANES AS AKT PROTEIN KINASE INHIBITORS
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The present invention provides compounds of Formula (I), including tautomers, resolved enantiomers, diastereomers, solvates, metabolites, salts and pharmaceutically acceptable prodrugs thereof. Also provided are methods of using the compounds of this invention as AKT protein kinase inhibitors and for the treatment of hyperproliferative diseases such as cancer.
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Page/Page column 75
(2009/03/07)
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- Spectroscopic, quantum chemical DFT/HF study and synthesis of [2.2.1] hept-2′-en-2′-amino-N-azatricyclo [3.2.1.02,4] octane
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The compound 4-N-bicyclo [2.2.1] hept-2′-en-2′-amino-N-azatricyclo [3.2.1.02,4] octane (2) has been synthesized and characterized by elemental analysis, IR, UV-vis, mass and NMR. Density functional theory (DFT) and Hartree-Fock (HF) calculations have been carried out for the title compound by using the standard 6-31G* basis set. The calculated results show that the predicted geometry can well reproduce the structural parameters. Predicted vibrational frequencies have been assigned and compared with experimental IR spectra and they complement each other. The theoretical electronic absorption spectra have been calculated by using CIS, TD-DFT and ZINDO methods. The 13C NMR and 1H NMR of compound (2) have been calculated by means of Becke 3-Lee-Yang-Parr (B3LYP) density functional method with 6-31G* basis set. Comparison between the experimental and the theoretical results indicates that density functional B3LYP method is able to provide satisfactory results for predicting NMR properties. On the basis of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated.
- Teimouri, Abbas,Emami, Mohammad,Chermahini, Alireza Najafi,Dabbagh, Hossein A.
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experimental part
p. 1749 - 1755
(2009/03/12)
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- Synthesis, characterization, and DFT studies of a novel azo dye derived from racemic or optically active binaphthol
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We present a new azo reactive dye from racemic or optically active BINOL. This dye was characterized by UV-vis, FTIR, mass, 1H NMR, and 13C NMR spectroscopic techniques and elemental analysis. The structure and spectrometry of this azo dye have been investigated theoretically by performing HF and DFT levels of theory using the standard 6-31G* basis set. The optimized geometries and calculated vibrational frequencies are evaluated via comparison with experimental values. The vibrational spectral data obtained from solid phase FTIR spectra are assigned based on the results of the theoretical calculations. The theoretical electronic absorption spectra have been calculated using CIS, TD-DFT, and ZINDO methods. In addition, a good agreement between calculated and experimental NMR data is observed.
- Teimouri, Abbas,Chermahini, Alireza Najafi,Emami, Mohammad
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experimental part
p. 11776 - 11782
(2009/04/05)
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- Bcl-XL-templated assembly of its own protein-protein interaction modulator from fragments decorated with thio acids and sulfonyl azides
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Protein-protein interactions have key importance in various biological processes and modulation of particular protein-protein interactions has been shown to have therapeutic effects. However, disrupting or modulating protein-protein interactions with low-molecular-weight compounds is extremely difficult due to the lack of deep binding pockets on protein surfaces. Herein we describe the development of an unprecedented lead synthesis and discovery method that generates only biologically active compounds from a library of reactive fragments. Using the protein Bcl-XL, a central regulator of programmed cell death, we demonstrated that an amidation reaction between thio acids and sulfonyl azides is applicable for Bcl-XL-templated assembly of inhibitory compounds. We have demonstrated for the first time that kinetic target-guided synthesis can be applied not only on enzymatic targets but also for the discovery of small molecules modulating protein-protein interactions. Copyright
- Hu, Xiangdong,Sun, Jiazhi,Wang, Hong-Gang,Manetsch, Roman
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supporting information; experimental part
p. 13820 - 13821
(2009/02/07)
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- Convenient one-pot synthesis of sulfonyl azides from sulfonic acids
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We have developed a one-pot process for preparing sulfonyl azides by treating sulfonic acids with trichloroacetonitrile, triphenylphosphine, and sodium azide at room temperature. A wide range of sulfonyl azides was synthesized in excellent yields under mild conditions. Georg Thieme Verlag Stuttgart.
- Kim, Joong-Gon,Doo, Ok Jang
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experimental part
p. 2885 - 2887
(2009/04/21)
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- SODIUM BOROHYDRIDE REDUCTION OF AROMATIC SULFONYL AZIDES IN THE PRESENCE OR ABSENCE OF TELLURIUM
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Some aromatic sulfonyl azides have been reduced, in various solvents, with sodium borohydride, in the presence or absence of Te element to the corresponding sulfonamides.Other functionals groups like the imino group may also be reduced.
- Obafemi, Craig. A.,Onigbinde, Adebayo O.
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- DIAZOTRANSFER REACTIONS WITH p-ACETAMIDOBENZENESULFONYL AZIDE
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The utility of p-acetamidobenzenesulfonyl azide in diazotransfer reactions is described.The practical, cost effective reagent offers advantages over existing alternatives.
- Baum, Jonathan S.,Shook, David A.,Daries, Huw M. L.,Smith, H. David
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p. 1709 - 1716
(2007/10/02)
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- N-Azidosulfonylaryl-maleinimides
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The invention relates to new arylsulfonylazides as well as the use of these compounds. The new compounds are characterized by the general formula: STR1 where R=aryl; x=1 or 2; and R1 and R2 are selected from H, CH3 and Cl and may be the same or different, with the provision that CH3 and Cl are not present side by side. The compounds according to the invention are suitable as photoinitiators in the preparation of relief structures by phototechniques from olefinically unsaturated polymers, as well as cross-link enhancing agents in the radical-wise cross linking of thermoplastic polymers.
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