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121.
Marcin Konkol Tetsuya Kohno Tatsuya Miyatake 《Journal of organometallic chemistry》2011,696(9):1792-2956
The tetradentate [OSSO]-type bis(phenol) ligands, [{2,2′-(HOC6H2-4,6-R2)2CH2SCH2CH2SCH2}] (R = tBu, 2; Br, 3) react with MBz4 (M = Zr, Hf) to yield the corresponding dibenzyl complexes, [M{2,2′-(OC6H2-4,6-R2)2CH2SCH2CH2SCH2}Bz2] (R = Br, M = Zr, 4Br; Hf, 5Br; R = tBu, M = Hf, 5) in a good to very good yield. Zirconium diamido complexes, [Zr{2,2′-(OC6H2-4,6-R2)2CH2SCH2CH2SCH2}(NMe2)2] (R = tBu, 6; Br, 6Br) were prepared in a reaction of the corresponding disodium salt of 2 or 3 generated in situ with ZrCl2(NMe2)2(THF)2. Heating of 6 with TMSCl at 35 °C afforded zirconium dichloro complex, [Zr{2,2′-(OC6H2-4,6-tBu2)2CH2SCH2CH2SCH2}Cl2] (7), whereas the titanium analog 8 was prepared in a direct reaction with TiCl4. While for complexes 4Br, 5, 5Br, 6, 6Br and 7 single C2-symmetric isomers were observed in solution at room temperature, as revealed by the NMR spectroscopic data, titanium complex 8 formed as a mixture of cis-α (8a) and cis-β (8b) isomers in a ratio of approx. 20:80% (measured in CD2Cl2). The VT NMR studies revealed a reversible conversion of 8a into 8b above 60 °C. The X-ray crystal structure determination of complexes 4Br, 5Br and 7 confirmed their C2-symmetrical configuration in the solid state with cis-arranged benzyl/chloro groups and the trans-coordination of two bulky phenolato moieties. The zirconium dibenzyl complexes exhibit good catalytic activities in homopolymerization of 1-hexene (atactic poly(1-hexene), PDI = 1.5-1.7) and vinylcyclohexane (isotactic poly(vinylcyclohexane), PDI = 1.2-1.8) upon activation with a co-catalyst. In both polymerizations no increase of activity was observed for the complex 4Br with electron-withdrawing substituents on phenolate rings. Moreover, polymerization of liquid propylene catalyzed by the titanium dichloro isomeric mixture 8 afforded at 5 °C ultrahigh molecular weight atactic/isotactic polypropylene mixtures. 相似文献
122.
The mechanism and dynamics of the formation of a hydrogen molecule by incorporating two hydrogen atoms in a stepwise manner into the cavity of some POSS (polyhedral oligomeric silsesquioxanes) compounds has been investigated by ab initio molecular orbital and ab initio molecular dynamics (AIMD) methods. The host molecules in the present reactions are two types of POSS, T(8) ([HSiO(1.5)](8)) and T(12)(D(2d)) ([HSiO(1.5)](12)). AIMD simulations were performed at the CASSCF level of theory, in which two electrons and two orbitals of the colliding hydrogen atoms are included in the active space. The trajectories were started by inserting the second hydrogen atom into the hydrogen atom-encapsulated-POSS (H + H@T(n) → H(2)@T(n); n = 8 and 12). In many cases, the gradual formation of a hydrogen molecule has been observed after frequent collisions of two hydrogen atoms within the cages. The effect of the introduction of an argon atom in T(12) is discussed as well. 相似文献
123.
A room temperature copper-catalyzed annulative amination of ortho-alkynylphenols with electrophilic amination reagents, O-acylated hydroxylamines, proceeds efficiently to provide the corresponding 3-aminobenzofurans of biological and pharmaceutical interest. 相似文献
124.
The L-epi-capreomycidine (Cpm) derivatives were efficiently and stereoselectively synthesized via nitrene C-H insertion starting from a readily available D-Tyr. Design of a substrate that takes into account hydrogen bonding is a critical feature in order to achieve high selectivity. Our synthetic strategy could be a new access to epi-Cpm and its derivatives, which are found in several biologically active natural products. 相似文献
125.
Progress toward the total synthesis of hederacines A and B is described. Our approach involves an allylic cyanate-to-isocyanate rearrangement, eneyne ring-closing metathesis, and a transannular reaction between the C-5 amino group and the C-12 position of the perhydroazuleno[5,6-b]furanone intermediate. 相似文献
126.
The direct dehydrogenative C-N coupling of azoles or polyfluoroarenes with N-H sulfoximines proceeds effectively in the presence of a copper catalyst at room temperature under air to afford the corresponding N-arylsulfoximines in good to high yields. 相似文献
127.
A boat-shaped glucopyranosyl nucleic acid (BsNA) was synthesized to investigate the possibility that the lean of a nucleobase is a factor affecting duplex-forming ability of oligonucleotides. From the crystal structure of a BsNA nucleoside and the thermal stability of duplex oligonucleotides, it was found that not only the lean of the base but also the rotation angle of the glycosidic bond axis were important factors in a stable duplex formation. 相似文献
128.
Ogawa T Hattori H Kaneko R Ito K Iwai M Mizutani Y Arinobu T Ishii A Seno H 《Analytical and bioanalytical chemistry》2011,400(7):1959-1965
In this report, a high-throughput and sensitive method for analysis of eight central-acting muscle relaxants in human plasma
by ultra-performance liquid chromatography–tandem mass spectrometry (UPLC-MS/MS) in the positive and negative ionization modes
using tolbutamide as internal standard is presented. After pretreatment of a plasma sample by solid-phase extraction with
an Oasis HLB cartridge, muscle relaxants were analyzed by UPLC with Acquity UPLC BEH C18 column and Acquity TQD tandem quadrupole mass spectrometer equipped with an electrospray ionization interface. The calibration
curves for muscle relaxants spiked into human plasma equally showed good linearities in the nanogram per milliliter order
range. The detection limits (signal-to-noise ratio = 3) was as low as 0.1–2 ng/mL. The method gave satisfactory recovery rates,
accuracy, and precision for quality control samples spiked with muscle relaxants. To further validate the present method,
250 mg of chlorphenesin carbamate was orally administered to a healthy male volunteer, and the concentrations of chlorphenesin
carbamate in plasma were measured 0.5, 1, 2, 4, 6, and 8 h after dosing; their concentrations in human plasma were between
0.62 and 2.44 μg/mL. To our knowledge, this is the first report describing simultaneous analysis of over more than two central-acting
muscle relaxants by liquid chromatography–tandem mass spectrometry. This has been realized by the capability of our instrument
for simultaneous multiple reaction monitoring of the target compounds in both positive and negative ionization modes. Therefore,
the present method seems very useful in forensic and clinical toxicology and pharmacokinetic studies. 相似文献
129.
Ishida Y Shimada T Masui D Tachibana H Inoue H Takagi S 《Journal of the American Chemical Society》2011,133(36):14280-14286
The quantitative excited energy transfer reaction between cationic porphyrins on an anionic clay surface was successfully achieved. The efficiency reached up to ca. 100% owing to the "Size-Matching Rule" as described in the text. It was revealed that the important factors for the efficient energy transfer reaction are (i) suppression of the self-quenching between adjacent dyes, and (ii) suppression of the segregated adsorption structure of two kinds of dyes on the clay surface. By examining many different kinds of porphyrins, we found that tetrakis(1-methylpyridinium-3-yl) porphyrin (m-TMPyP) and tetrakis(1-methylpyridinium-4-yl) porphyrin (p-TMPyP) are the suitable porphyrins to accomplish a quantitative energy transfer reaction. These findings indicate that the clay/porphyrin complexes are promising and prospective candidates to be used for construction of an efficient artificial light-harvesting system. 相似文献
130.
Yamaguchi K Ueki R Nonaka H Sugihara F Matsuda T Sando S 《Journal of the American Chemical Society》2011,133(36):14208-14211
Monoamine oxidase (MAO) A is a flavoenzyme that catalyzes the oxidation of biologically important monoamines and is thought to be associated with psychiatric disorders. Here, we report a strategy for rationally designing a (19)F magnetic resonance imaging probe for the specific detection of human MAO-A (hMAO-A) activity. Our designed (19)F probe was oxidized expeditiously by hMAO-A to produce 2-fluoro-4-nitrophenol via a spontaneous β-elimination mechanism. Concomitant with the structural change of the probe to the product, the (19)F chemical shift changed by 4.2 ppm, which was enough to visualize the probe and enzymatic product separately. Importantly, our probe achieved excellent discrimination of hMAO-A from its isoform hMAO-B. 相似文献