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  • 11
    ISSN: 0899-0042
    Keywords: chiral recognition mechanisms ; quantitative structure ; enantioselective retention relationships ; chiral chromatography ; enantioselective separations ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of 12 chiral arylcarboxylic acids were chromatographed on an immobilized human serum albumin chiral stationary phase (HSA-CSP). The effects of solute structure on chromatographic retentions and enantioselective separations were examined by linear regression analysis and the construction of quantitative structure-enantioselective retention relationships. Competitive displacement studies were also conducted using R-ibuprofen as the displacing agent. The results indicate that the enantioselective retention of the solutes takes place at the indole-benzodiazepine site (site II) on the HSA molecule and that chiral recognition is affected by the hydrophobicity and steric volume of the solutes. The displacement studies also identified a cooperative allosteric interaction induced by the binding of R-ibuprofen to site II. Chirality 9:178-183, 1997. © 1997 Wiley-Liss, Inc.
    Additional Material: 4 Ill.
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  • 12
    ISSN: 0899-0042
    Keywords: asymmetric induction ; circular dichroism ; Cotton effect ; dialdo carbohydrate derivative ; diastereo-selectivity ; diastereozero-plane ; ellipticity exaltation ; IR spectroscopy ; magnesium enediolate ; relative configuration ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To control stereoselectivity in aldol-like reactions with chiral carbohydrate templates, we studied the interaction between completely protected dialdo compounds and magnesium enediolates of arylacetic acids. Diastereomeric mixtures of the highly functionalized acids obtained were esterified to isolate individual methyl uronates. It was found that all the diastereomeric esters exhibit Cotton effects of the same positive sign in the 220-230 nm region and so possess the same S configuration of the aryl chiral center C(6). Chiral center C(5) configurational assignments were performed using IR and ORD spectroscopy. We separated and specified four pairs of diastereomeric methyl uronates. It follows that the precursory acids have the same 5R*, 6S (major isomers) and 5S*, 6S (minor isomers) configurations. A tentative mechanism for complexation and possible models of Mg2+ -protected dialdose intermediate complexes has been proposed. We have concluded that a kind of orbital steering is realized, accompanied by some “tuning” of molecular assembly conditioned by two-point coordination between Mg2+ and potential cation-binding sites in the substrate molecules. Thus it has been demonstrated that reasonable diastereo-selectivity can be achieved even through the use of small matrix molecules using rather small functional groups, which do not impose any stringent steric requirements. © 1993 Wiley-Liss, Inc.
    Additional Material: 11 Ill.
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  • 13
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nucleophilic substitution of 6β-chloro-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan (1) and 8α-bromo-6,7-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan (2) with lithium cyano(methyl)- and (aryl)cyanocuprates(I) (5a-c) was accompanied by allylic rearrangement with both change and retention of orientation of the substituting group (Scheme 1, Table 1). Nucleophilic substitution in 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan-6α-yl methanesulfonate (3) and 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan-6β-yl methanesulfonate (4) proceeded without allylic rearrangement with both change and retention of the orientation of the substituting group (Scheme 2, Table 1). X-Ray diffraction studies of the products 6,7-didehydro-4,5α-epoxy-3-methoxy-17-methyl-8α-phenylmorphinan (6b) and 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methyl-6β-phenylmorphinan (7b) were carried out (Figs. 1 and 2).
    Additional Material: 2 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 2 (1988), S. 533-537 
    ISSN: 0268-2605
    Keywords: Polymerization ; ethynylferrocene ; conductivity ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The catalytic activity of the [Rh(cod)Cl]2 complex (cod = cis, cis-cyclo-octa-1,5-diene) with respect to the polymerization of ethynylferrocene (EFc) was examined. A good yield (about 80%) of polyethynylferrocene (PEFc) was obtained in benzene by addition of sodium hydroxide as co-catalyst. PEFc was insoluble in most organic solvents. The conductivity (s̰) of the undoped polymer is about 10-11 ohm-1 cm-1; upon doping PEFc with iodine in tetrahydrofuran the conductivity can be increased to 10-100 ohm-1 cm-1. The influence of other doping agents was also examined.
    Additional Material: 2 Ill.
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  • 15
    ISSN: 0268-2605
    Keywords: Bis(ferrocenylalkyl)azolium cations ; experimental tumors ; virus-induced Rauscher leukemia ; cytotoxicity ; antitumor effect ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the basis of an earlier model of chemical carcinogenesis, the antitumor activity of the mono-, bi- and poly-nuclear ferrocene derivatives ferricenium tri-iodide (1), ferricenium tetrachloroferrate (2), 1, 1′-diethylferricenium triiodide: (3), N-(ferrocenylmethyl)hexamethylenetetramine tetrafluoroborate (4), bis(ferrocenylmethyl)benzotriazolium tetrafluoroborate (5), bis(ferrocenyl-α-ethyl)benzotriazolium tetrafluoroborate (6) and bis(ferrocenylmethyl)-2-methylbenzimidazolium tetrafluoroborate (7), and the oligomer ( - Fc - CH2 - Fc+· - CH2 - )7-8- (PF6)7-8 (8) was studied in vivo (Fc=C10H8Fe). The tumor models studied included MCH-11 (mouse sarcoma induced by methylcholantrene), P-815 (mouse mastocytoma of DBA/2 origin) and virus-induced Raucher leukemia (RLV). The cytotoxic effects of these preparations were examined against in vitro cultured normal murine cells (line L-929). The binuclear ferrocene derivatives 5, 6 and 7 inhibited the development of experimental tumors in mice. Ferricenium tri-iodide (1) was effective in Rauscher leukemia. Kinetic dependencies for most complexes had a two-phase character: the region of inhibition of tumorogenesis was followed by a region in which the complexes accelerated the development of this process. The link between the structure of compounds 1-8 and their antitumor effects is discussed.
    Additional Material: 12 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 4 (1990), S. 77-89 
    ISSN: 0268-2605
    Keywords: Gas chromatography ; liquid chromatography ; Group IV ; detectors ; separation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chromatographic aspects of the analysis of Group IV organometallic derivatives are reviewed. The emphasis is towards gas and liquid chromatography.
    Additional Material: 2 Tab.
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  • 17
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 4 (1990), S. 163-172 
    ISSN: 0268-2605
    Keywords: Organopolysilanes ; organopolysiloxanes ; photoinitiation ; vulcanization ; thin films ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The organopolysilanes Me(Me2Si)nMe (n = 4-6), (Me2Si)6 and (Me3Si)2SiMePh are found to be effective photoinitiators for the polymerization of vinyl-containing siloxane rubbers. The trisilanes Me(ME2Si)3Me and Me3SiSiMe2SiMe2Ph are slightly effective, while phenyldisilanes do not exhibit initiation activity in the process of photocuring. Polydimethylsiloxanes are cured at a slower rate under the same conditions than vinylcontaining derivatives. Two mechanisms of crosslinking are proposed: silylene-silirane-silanol and silylene-hydride-silanol.
    Additional Material: 1 Tab.
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  • 18
    ISSN: 0170-2041
    Keywords: Thymidine derivatives ; Azides ; HIV ; Carbohydrates ; Nucleosides ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Compound 15 - the 2′-azido analog of the anti-HIV compound 2′,3′-didehydro-2′,3′-dideoxythymidine - was synthesized. Treatment of 5′-O-trityl-β-D-ribofuranosylthymine (1) with DAST or MSTF gave the 2,2′-anhydro derivative 2. The latter and its 3′-O-benzoate 3 were used for the synthesis of the 2′-azido-2′-deoxy derivatives 4 and 5. Two routes to the synthesis of 15 from 5 were investigated. (i) Treatment of 5 with DAST gave a mixture of the 5′-O-trityl derivatives 12 and 13 as well as 1-(2-azido-2,3-dideoxy-3-fluoro-β-D-xylofuranosyl)thymine (16) along with 2,3′-anhydro derivative 14 (2%). Detritylation of the mixture yielded 15 (39%) and 16 (12%). (ii) Mesylation of 5 gave 17 which yielded 15 upon saponification and detritylation. Compound 15 showed moderate inhibitory activity against HIV-1 and HIV-2 in MT-4 cells.
    Additional Material: 4 Tab.
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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 159 (1871), S. 247-251 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 20
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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