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941.
《Journal of carbohydrate chemistry》2013,32(3):237-250
1‐(2,3,4‐tri‐O‐acety‐6‐azido‐6‐deoxy‐5‐thio‐β‐D‐glucopyranosyl)thymine 5 and the 6‐thio‐septanosylthymine analogue 7 were obtained via the intramolecular displacement of the corresponding tosylate 2 by azide. Alternatively, 5 was obtained from bromination of alcohol 1 in the presence of azide. Deblocking of 5 afforded the nucleoside 6. Glycosylation of the tetraacetate 11, obtained by acetolysis of 10 with thymine, afforded the 3‐O‐tosyl‐β‐D‐glucopyranosylthymine derivative 13, which furnished the 3‐azido‐3‐deoxy‐β‐D‐allopyranosyl‐thymine analogue 14 on reaction with azide ion. Alternatively, the glucoside 12 gave the corresponding gluco analogue 16 on treatment with azide. Acetolysis of 16 furnished the tetraacetate 17, which was subjected for glycosylation to give the gluco nucleoside 18. Deblocking of 14 and 18 afforded the free 3‐azido‐nucleosides 15 and 19, respectively. The isothionucleoside 21 was prepared from treatment of thymine with the 2,3‐epoxide derivative 20 in the presence of Ti(i‐PrO)4 and triethyl amine. Mild acid hydrolysis of 21 afforded 22. Cycloaddition of the 2‐azido‐altroside 23 with dimethyl acetylenedicarboxylate gave the 1,2,3‐triazole derivative 24. Treatment of 24 with methanolic ammonia afforded the 4,5‐carboxamide analogue 25. The conformations of the new products were studied by NMR spectroscopy. 相似文献
942.
Carboxymethyl chitosan was grafted with N-acryloyl,N′-cyanoacetohydrazide in homogenous aqueous phase using potassium persulfate initiator. The maximum grafting yield achieved was 448% at 0.03 mol/L potassium persulfate, 0.75 mol/L N-acryloyl,N′-cyanoacetohydrazide, and 60°C within 2 h. The grafted copolymers showed better thermal stability than that of carboxymethyl chitosan. The samples with percent grafting values up to 98% were soluble in water, but a higher grafting extent resulted in insoluble copolymers. The grafted copolymers are nontoxic materials and showed an inhibition effect on both Escherichia coli and Staphylococcus aureus bacteria and Aspergillus flavus and Candida albicans fungi better than those of chitosan and carboxymethyl chitosan themselves. 相似文献
943.
Chadi Khoury François Le Goffic Marie‐Noëlle Rager 《Journal of carbohydrate chemistry》2013,32(7):395-409
The synthesis of 2‐acetamido‐2‐deoxy‐6‐O‐octanoyl‐D‐glucono‐1,5‐lactone 9 and 2‐acetamido‐2‐deoxy‐6‐O‐octanoyl‐α‐D‐glucopyranose 7 from 2‐acetamido‐2‐deoxy‐α‐D‐glucopyranose is reported. For both targets, the key intermediate was allyl 2‐acetamido‐3,4‐di‐O‐benzyl‐2‐deoxy‐6‐O‐octanoyl‐α‐D‐glucopyranoside 5. Surface tension measurements (critical micellar concentration of 22.3 mM and 5 mM for 9 and 7, respectively) showed up the surface activity of both compounds, while enzyme inhibition assays indicated that 9 could inhibit bovine β‐N‐acetylglucosaminidase (Ki=6.5 µM) but not Serratia marcescens chitobiase nor hen egg‐white lysozyme. Moreover, 7 was shown to induce chitinase production of S. marcescens and to be readily metabolized by these bacteria. 相似文献
944.
Raman Tandon Teresa Unzner Dr. Tobias A. Nigst Dr. Nicolas De Rycke Dr. Peter Mayer Dr. Bernd Wendt Dr. Olivier R. P. David Prof. Dr. Hendrik Zipse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(20):6435-6442
New heterocyclic derivatives of 9‐azajulolidine have been synthesized and characterized with respect to their nucleophilicity and Lewis basicity. The Lewis basicity of these bases as quantified through their theoretically calculated methyl‐cation affinities correlate well with the experimentally measured reaction rates for addition to benzhydryl cations. All newly synthesized pyridines show exceptional catalytic activities in benchmark acylation reactions, which correlate only poorly with Lewis basicity or nucleophilicity parameters. A combination of Lewis basicity with charge and geometric parameters in the framework of a three‐component quantitative structure–activity relationship (QSAR) model is, however, highly predictive. 相似文献
945.
Dr. Christoph W. Wullschleger Prof. Dr. Jürg Gertsch Prof. Dr. Karl‐Heinz Altmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(39):13105-13111
The stereoselective syntheses of 7,8,9‐trideoxypeloruside A ( 4 ) and a monocyclic peloruside A analogue lacking the entire tetrahydropyran moiety ( 3 ) are described. The syntheses proceeded through the PMB‐ether of an ω‐hydroxy β‐keto aldehyde as a common intermediate which was elaborated into a pair of diastereomeric 1,3‐syn and ‐anti diols by stereoselective Duthaler–Hafner allylations and subsequent 1,3‐syn or anti reduction. One of these isomers was further converted into a tetrahydropyran derivative in a high‐yielding Prins reaction, to provide the precursor for bicyclic analogue 4 . Downstream steps for both syntheses included the substrate‐controlled addition of a vinyl lithium intermediate to an aldehyde, thus connecting the peloruside side chain to C15 (C13) of the macrocyclic core structure in a fully stereoselective fashion. In the case of monocyclic 3 macrocyclization was based on ring‐closing olefin metathesis (RCM), while bicyclic 4 was cyclized through Yamaguchi‐type macrolactonization. The macrolactonization step was surprisingly difficult and was accompanied by extensive cyclic dimer formation. Peloruside A analogues 3 and 4 inhibited the proliferation of human cancer cell lines in vitro with micromolar and sub‐micromolar IC50 values, respectively. The higher potency of 4 highlights the importance of the bicyclic core structure of peloruside A for nM biological activity. 相似文献
946.
Dr. Manivannan Ethirajan Dr. Ping Chen Dr. Tymish Y. Ohulchanskyy Dr. Lalit N. Goswami Dr. Anurag Gupta Dr. Avinash Srivatsan Dr. Mahabeer P. Dobhal Joseph R. Missert Prof. Paras N. Prasad Prof. Karl M. Kadish Prof. Ravindra K. Pandey 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6670-6684
We report herein a simple and efficient approach to the synthesis of a variety of meso‐substituted purpurinimides. The reaction of meso ‐ substituted purpurinimide with N‐bromosuccinimide regioselectively introduced a bromo functionality at the 20‐position, which on further reaction with a variety of boronic acids under Suzuki reaction conditions yielded the corresponding meso‐substituted analogues. Interestingly, the free base and the metalated analogues showed remarkable differences in photosensitizing efficacy (PDT) and tumor‐imaging ability. For example, the free‐base conjugate showed significant in vitro PDT efficacy, but limited tumor avidity in mice bearing tumors, whereas the corresponding NiII derivative did not produce any cell kill, but showed excellent tumor‐imaging ability at a dose of 0.3 μmol kg?1 at 24, 48, and 72 h post‐injection. The limited PDT efficacy of the NiII analogue could be due to its inability to produce singlet oxygen, a key cytotoxic agent required for cell kill in PDT. Based on electrochemical and spectroelectrochemical data in DMSO, the first one‐electron oxidation (0.52 V vs. SCE) and the first one‐electron reduction (?0.57–0.67 V vs. SCE) of both the free base and the corresponding NiII conjugates are centered on the cyanine dye, whereas the second one‐electron reduction (?0.81 V vs. SCE) of the two conjugates is assigned to the purpurinimide part of the molecule. Reduction of the cyanine dye unit is facile and occurs prior to reduction of the purpurinimide group, which suggests that the cyanine dye unit as an oxidant could be the driving force for quenching of the excited triplet state of the molecules. An interaction between the cyanine dye and the purpurinimide group is clearly observed in the free‐base conjugate, which compares with a negligible interaction between the two functional groups in the NiII conjugate. As a result, the larger HOMO–LUMO gap of the free‐base conjugate and the corresponding smaller quenching constant is a reason to decrease the intramolecular quenching process and increase the production of singlet oxygen to some degree. 相似文献
947.
948.
Dr. Xiangheng Niu Prof. Dr. Minbo Lan Dr. Hongli Zhao Dr. Chen Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(29):9534-9541
The investigation of highly efficient catalysts for the electrochemical oxidation of glucose is the most critical challenge to commercialize nonenzymatic glucose sensors, which display a few attractive superiorities including the sufficient stability of their properties and the desired reproducibility of results over enzyme electrodes. Herein we propose a new and very promising catalyst: Pt cubes well‐dispersed on the porous Cu foam, for the the electrochemical oxidation reaction of glucose in neutral media. The catalyst is fabricated in situ on a homemade screen‐printed carbon electrode (SPCE) substrate through initially synthesizing the three‐dimensional (3D) porous Cu foam using a hydrogen evolution assisted electrodeposition strategy, followed by electrochemically reducing the platinic precursor simply and conveniently. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) proofs demonstrate that Pt cubes, with an average size (the distance of opposite faces) of 185.1 nm, highly dispersed on the macro/nanopore integrated Cu foam support can be reproducibly obtained. The results of electrochemical tests indicate that the cubic Pt‐based catalyst exhibits significant enhancement on the catalytic activity towards the electrooxidation of glucose in the presence of chloride ions, providing a specific activity 6.7 times and a mass activity 5.3 times those of commercial Pt/C catalysts at ?0.4 V (vs. Ag/AgCl). In addition, the proposed catalyst shows excellent stability of performance, with only a 2.8 % loss of electrocatalytic activity after 100 repetitive measurements. 相似文献
949.
Dr. Umesh A. Kshirsagar Regev Parnes Hagit Goldshtein Dr. Rivka Ofir Dr. Raz Zarivach Dr. Doron Pappo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13575-13583
An iron‐based cross‐dehydrogenative coupling (CDC) approach was applied for the diversity‐oriented synthesis of coumestrol‐based selective estrogen receptor modulators (SERMs), representing the first application of CDC chemistry in natural product synthesis. The first stage of the two‐step synthesis of coumestrol involved a modified aerobic oxidative cross‐coupling between ethyl 2‐(2,4‐dimethoxybenzoyl)acetate and 3‐methoxyphenol, with FeCl3 (10 mol %) as the catalyst. The benzofuran coupling product was then subjected to sequential deprotection and lactonization steps, affording the natural product in 59 % overall yield. Based on this new methodology other coumestrol analogues were prepared, and their effects on the proliferation of the estrogen receptor (ER)‐dependent MCF‐7 and of the ER‐independent MDA‐MB‐231 breast cancer cells were tested. As a result, new types of estrogen receptor ligands having an acetamide group instead of the 9‐hydroxyl group of coumestrol were discovered. Both 9‐acetamido‐coumestrol and 8‐acetamidocoumestrol were found more active than the natural product against estrogen‐dependent MCF‐7 breast cancer cells, with IC50 values of 30 and 9 nM , respectively. 相似文献
950.
Dr. Madleen Busse Iman Trinh Prof. Peter C. Junk Assoc. Prof. Richard L. Ferrero Prof. Philip C. Andrews 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(17):5264-5275
The synthesis and characterisation of nine new tris‐substituted bismuth(III) aminoarenesulfonates of the general formula [Bi(O3S‐RN)3] (RN=o‐aminophenyl 1 , m‐aminophenyl 2 , 6‐amino‐3‐methoxyphenyl 3 , p‐aminophenyl 4 , 2‐pyridyl 5 , o‐aminonaphthyl 6 , 5‐aminonaphthyl 7 , 4‐amino‐3‐hydroxynaphthyl 8 and 5‐isoquinolinyl 9 ) is described. Two synthetic strategies, using Ag2O and [Bi(OtBu)3], were explored and compared. The possibility to access heteroleptic bismuth(III) complexes with the new silver(I) metathesis reaction is demonstrated with the synthesis of the heteroleptic bismuth(III) aminoarenesulfonate complexes [PhBi(O3S‐P2)2(dmso)] 10 , [Ph2Bi(O3S‐P2)]∞ 11 and [PhBi(O3S‐P2)2]∞ 12 , of which the solid state structures 10 and 12 are presented (2P‐SO3?=2‐pyridinesulfonate). These complexes offer remarkable in‐vitro activity against three standard laboratory strains of Helicobacter pylori (H. pylori) as demonstrated by their exceptionally low minimum inhibitory concentration (MIC) values of 0.049 μg mL?1 for the strains 251 and B128, which places most MIC values in the nano‐molar region. These results demonstrate the importance of the amino functionality in addition to the sulfonate group on the bactericidal properties against H. pylori. 相似文献