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21.
Lukin O Müller WM Müller U Kaufmann A Schmidt C Leszczynski J Vögtle F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3507-3517
The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents. 相似文献
22.
Fry FH Holme AL Giles NM Giles GI Collins C Holt K Pariagh S Gelbrich T Hursthouse MB Gutowski NJ Jacob C 《Organic & biomolecular chemistry》2005,3(14):2579-2587
Certain cancer cells proliferate under conditions of oxidative stress (OS) and might therefore be selectively targeted by redox catalysts. Among these catalysts, compounds containing a chalcogen and a quinone redox centre are particularly well suited to respond to the presence of OS. These catalysts combine the specific electrochemical features of quinones and chalcogens. They exhibit high selectivity and efficiency against oxidatively stressed rat PC12, human Jurkat and human Daudi cells in cell culture, where their mode of action most likely involves the catalytic activation of existent and the generation of new reactive oxygen species. The high efficiency and selectivity shown by these catalysts makes them interesting for the development of anti-cancer drugs. 相似文献
23.
Thoma G Streiff MB Katopodis AG Duthaler RO Voelcker NH Ehrhardt C Masson C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(1):99-117
Polyvalent carbohydrate-protein interactions occur frequently in biology, particularly in recognition events on cellular membranes. Collectively, they can be much stronger than corresponding monovalent interactions, rendering it difficult to control them with individual small molecules. Artificial macromolecules have been used as polyvalent ligands to inhibit polyvalent processes; however, both reproducible synthesis and appropriate characterization of such complex entities is demanding. Herein, we present an alternative concept avoiding conventional macromolecules. Small glycodendrimers which fulfill single molecule entity criteria self-assemble to form non-covalent nanoparticles. These particles-not the individual molecules-function as polyvalent ligands, efficiently inhibiting polyvalent processes both in vitro and in vivo. The synthesis and characterization of these glycodendrimers is described in detail. Furthermore, we report on the characterization of the non-covalent nanoparticles formed and on their biological evaluation. 相似文献
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The oxidation of 2,6-dichloro-3-benzylpyridines and bis(2,6-dichloro-3-pyridyl)methanes, respectively, was accomplished using chromic trioxide in a highly acidic medium. The synthesis of several phenyl-3-(2,6-dichloropyridyl)ketones and of bis(2,6-dichloro-3-pyridyl)ketone are reported. 相似文献
26.
Zusammenfassung Aus Anilinen, die im aromatischen Ring mit CH3, CH3SCH2, CH3O, Cl, Br oder NO2 substituiert sind, und Sulfoxiden wird in Anwesenheit von P4O10 und Triäthylamin eine Reihe von N-Aryl-S,S-dialkylsulfimiden erhalten. Diese Reihe umfaßt Verbindungen mit CH3-, C2H5- und –(CH2)4-Gruppen am Schwefelatom. Das Sulfimid aus Mesidin lagert sich—formal analog zu einerSommelet—Hauser-Umlagerung—zum 2,4,6-Trimethyl-2-methylthiomethylcyclohexa-3,5-dien-1-imin um.
Als 1. Mitt. soll gelten:P. Claus, Mh. Chem.99, 1034 (1968).
2. Mitt.:P. Claus undW. Vycudilik, Tetrahedron Letters1968, 3607. 相似文献
Methylthiomethylation of anilines and phenols, III: Preparation of N-aryl-S,S-dialkylsulfimides
The synthesis of a number of N-aryl-S,S-dialkylsulfimides by reaction of anilines with sulfoxides in presence of P4O10 and triethylamine is given. This series includes compounds with CH3-, CH3SCH2-, CH3O-, Cl-, Br- and nitro-groups attached to the aromatic nucleus, resp., and with CH3-, C2H5-or–(CH2)4-groups on the sulfur atom. The sulfimide obtained from mesidine is rearranged in formal analogy to aSommelet-Hauser rearrangement to 2.4.6-trimethyl-2-methylthio-methylcyclohexa-3.5-dien-1-imine.
Als 1. Mitt. soll gelten:P. Claus, Mh. Chem.99, 1034 (1968).
2. Mitt.:P. Claus undW. Vycudilik, Tetrahedron Letters1968, 3607. 相似文献
27.
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29.
Abe K Abt I Acton PD Agnew G Ash WW Aston D Bacchetta N Baird KG Baltay C Band HR Baranko G Bardon O Battiston R Bazarko AO Bean A Belcinski RJ Ben-David R Benvenuti AC Biasini M Bienz T Bilei GM Bisello D Blaylock G Bogart JR Bolton T Bower GR Brau JE Breidenbach M Bugg WM Burke D Burnett TH Burrows PN Busza W Calcaterra A Caldwell DO Calloway D Camanzi B Carpinelli M Carr J Cassell R Castaldi R Castro A Cavalli-Sforza M Chadwick GB Chen L Church E Claus R Cohn HO Coller JA Cook V Cotton R 《Physical review letters》1993,71(16):2528-2532
30.
LoSecco JM Bionta RM Biewitt G Bratton CB Casper D Chrysicopoulou P Claus R Cortez BG Errede S Foster GW Gajewski W Ganezer KS Goldhaber M Haines TJ Jones TW Kielczewska D Kropp WR Learned JG Lehmann E Park HS Reines F Schultz J Seidel S Shumard E Sinclair D Sobel HW Stone JL Sulak L Svoboda R van der Velde JC Wuest C 《Physical review letters》1985,54(21):2299-2301