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11.
Mária Meiarová Katarína Hubinská tefan Toma Burkhard Koch Albrecht Berkessel 《Monatshefte für Chemie / Chemical Monthly》2007,138(11):1181-1186
Summary.
N-Toluensulfonyl-l-prolin amide was tested as catalyst in the enantioselective Michael addition of carbonyl compounds to (E)-β-nitrostyrene in nine ionic liquids under different reaction conditions. The reaction rates and enantioselectivities were
strongly dependent on the ionic liquids. Change of enantioselectivity was observed too and it is attributed to both the cation
and the anion of ionic liquid. The best yields (up to 98%) and enantioselectivity (70% ee) of product were obtained in a basic ionic liquid [bmim]BF4 at room temperature. 相似文献
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15.
Wagner F Gruber O Lackner K Murmann HD Speth E Becker G Bosch HS Brocken H Cattanei G Dorst D Eberhagen A Elsner A Erckmann V Fussmann G Gehre O Gernhardt J Gierke Gv Glock E Grieger G Grigull P Haas G Hacker H Hartfuss HJ Jäckel H Jaenicke R Janeschitz G Junker J Karger F Kasparek W Keilhacker M Kick M Klüber O Kornherr M Kroiss H Kuehner M Lenoci M Lisitano G Maassberg M Mahn C Marlier S Mayer HM McCormick K Meisel D Mertens V Müller ER Müller Müller G Niedermeyer H Ohlendorf W 《Physical review letters》1986,56(20):2187-2190
16.
Albrecht H Binder U Harder G Lembke-Koppitz I Philipp A Schmidt-Parzefall W Schröder H Schulz HD Wurth R Donker JP Drescher A Matthiesen U Scheck H Spaan B Spengler J Wegener aD Gabriel JC Schubert KR Stiewe J Waldi R Weseler S Brown NN Edwards KW Frisken WR Fukunaga C Gilkinson DJ Gingrich DM Goddard M Kapitza H Kim PC Kutschke R MacFarlane DB McKenna JA McLean KW Nilsson AW Orr RS Padley P Patel PM Prentice JD Seywerd HC Stacey BJ Yoon T Yun JC Ammar R Coppage D Davis R Kanekal S Kwak N 《Physical review letters》1986,56(6):549-552
17.
Pegaz B Debefve E Borle F Ballini JP Wagnières G Spaniol S Albrecht V Scheglmann D Nifantiev NE van den Bergh H Konan YN 《Photochemistry and photobiology》2005,81(6):1505-1510
In the present study, photodynamic activity of a novel photosensitizer (PS), Chlorin e(6)-2.5 N-methyl-d-glucamine (BLC 1010), was evaluated using the chorioallantoic membrane (CAM) as an in vivo model. After intravenous (i.v.) injection of BLC 1010 into the CAM vasculature, the applicability of this drug for photodynamic therapy (PDT) was assessed in terms of fluorescence pharmacokinetics, i.e. leakage from the CAM vessels, and photothrombic activity. The influence of different PDT parameters including drug and light doses on the photodynamic activity of BLC 1010 has been investigated. It was found that, irrespective of drug dose, an identical continuous decrease in fluorescence contrast between the drug inside and outside the blood vessels was observed. The optimal treatment conditions leading to desired vascular damage were obtained by varying drug and light doses. Indeed, observable damage was achieved when irradiation was performed at light doses up to 5 J/cm(2) 1 min after i.v. injection of drug doses up to 0.5 mg/kg body weight(b.w.). However, when irradiation with light doses of more than 10 J/cm(2) was performed 1 min after injection of drug doses up to 2 mg/kg body weight, this led to occlusion of large blood vessels. It has been demonstrated that it is possible to obtain the desired vascular occlusion and stasis with BLC 1010 for different combinations of drug and/or light doses. 相似文献
18.
The hydrogenation of unsaturated organic substrates such as olefins and ketones is usually effected by homogeneous or heterogeneous transition-metal catalysts. On the other hand, a single case of a transition-metal-free and purely base-catalyzed hydrogenation of ketones was reported by Walling and Bollyky some 40 years ago. Unfortunately, the harsh reaction conditions (ca. 200 degrees C, >100 bar H(2), potassium tert-butoxide as base) limit the substrate spectrum of this reaction to robust, nonenolizable ketones such as benzophenone. We herein present a mechanistic study of this process as a basis for future rational improvement. The base-catalyzed hydrogenation of ketones was found to be irreversible, and it shows first-order kinetics with respect to the substrate ketone, hydrogen, and catalytic base. The rate of the reaction depends on the type of alkali ion present (Cs > Rb - K > Na > Li). Using D(2) instead of H(2) revealed a rapid base-catalyzed isotope exchange/equilibration between the gas phase and the solvent as a concomitant reaction. The degree of deuteration of the product alcohols did not indicate a significant kinetic isotope effect. It is proposed that both ketone reduction and isotope exchange proceed via similar six-membered cyclic transition states involving the H(2)(D(2))-molecule, the alkoxide base, and the ketone (solvent alcohol in the case of isotope exchange). Mechanistic analogies are pointed out which apparently exist between the base-catalyzed hydrogenation of ketones studied here and the Ru-catalyzed asymmetric ketone hydrogenation developed by Noyori. In both cases, heterolysis of the hydrogen molecule appears to be assisted by a Br?nsted-base (i.e., alkoxide), the latter being bound to the substrate ketone or the catalyst ligand, respectively, by a bridging Lewis-acidic alkali ion. 相似文献
19.
Most sedimentary rocks contain small concentrations of finely divided organic material. With the aid of modern analytical methods, samples of such rocks can be examined in detail, and conclusions can be drawn concerning the origin of the organic substances. Intact or modified biogenic compounds such as paraffins, isoprenoids, alcohols, ketones, carboxylic acids, steroids, triterpenes, and porphyrins have been isolated from the soluble fractions of the organic material of many sediments and from identified fossils of various geological ages. Even Precambrian rocks contain biogenic substances, so that life forms must have existed more than three billion years ago. The main component of the organic material is “kerogen”, the complicated polymeric structure of which has not yet been established. 相似文献
20.
Rodríguez G Albrecht M Schoenmaker J Ford A Lutz M Spek AL van Koten G 《Journal of the American Chemical Society》2002,124(18):5127-5138
The reactivity of the bifunctionalized ligand NC(Br)N-I 1 [IC(6)H(2)(CH(2)NMe(2))(2)-3,5-Br-4] has been studied as a versatile synthon for organic and/or organometallic synthesis. Chemoselective metalation (M = Pd, Pt, Li) at the C(aryl)-I or C(aryl)-Br bonds was achieved by choosing the appropriate metal precursors. In this way a series of Pt(II) and Pd(II) complexes were prepared that have a second functional group available for further reactions. These Pt(II) and Pd(II) complexes were subjected to a wide range of organic and organometallic reactions, revealing the remarkable stability of their M-C sigma-bond and opening an easy route for the synthesis of mono- and (hetero)bimetallic building blocks. The scope of the chemistry of such building blocks shows that they are good candidates for use in the synthesis of dendrimers, bioorganometallic systems, or polymetallic materials. The X-ray crystal structures of the most representative complexes (2, 3a, 19, 20, and 24) are also reported. 相似文献