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161.
162.
Kazuhiro Nagata Daisuke Sano Yu Shimizu Michiko Miyazaki Takuya Kanemitsu Takashi Itoh 《Tetrahedron: Asymmetry》2009,20(21):2530-2536
The catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates with an alkyl halide was performed under phase-transfer conditions to afford compounds which have a chiral quaternary carbon with up to 97% and 94% ee, respectively. As applications of this method, chiral 2-oxindole derivatives and a β-lactam derivative were synthesized. 相似文献
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165.
Daisuke Kamei Hiroharu Ajiro Mitsuru Akashi 《Journal of polymer science. Part A, Polymer chemistry》2010,48(16):3651-3657
The effects of stereoregularity, temperature, and solvent on the specific recognition of syndiotactic (st)‐poly(methacrylic acid) (PMAA) in macromolecularly porous isotactic (it)‐poly(methyl methacrylate) films were investigated to give important insights into the regularity and stability of nanospaces in the it‐PMMA films as well as template polymerization. The porous it‐PMMA films were fabricated on quartz crystal microbalance (QCM) substrates via the layer‐by‐layer (LbL) assembly of it‐PMMA/st‐PMAA, plus the st‐PMAA extraction from the assembly. QCM analysis and infrared spectroscopy revealed the first case of stereocomplex formation using st‐PMAA with lower stereoregularity (rr = 73%) in the LbL films, while st‐PMAA obtained with conventional free radical polymerization (rr = 62%) was barely incorporated into the porous it‐PMMA films. The maximum st‐PMAA incorporation increased from 25 to 40 °C, but there were almost no difference between 40 and 55 °C, indicating that the it‐PMMA crystallization would also be accelerated with increasing temperature. The studies on st‐PMAA incorporation with various complexing solvents revealed that the host it‐PMMA in the porous films could only form the original stereocomplex with 2/1 unit‐molar stoichiometry (st‐PMAA/it‐PMMA) in acetonitrile/water or ethanol/water. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3651–3657, 2010 相似文献
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167.
Daisuke Nagai Asuka Fujii Masayoshi Tanaka Bungo Ochiai Atsushi Sudo Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2009,47(6):1510-1521
Anionic polymerization of methacrylates under sterically confined environment in a spherical beads‐shaped networked polystyrene (NwPS) matrix is described. The initiator used herein is a samarium (Sm) (III) enolate, which was formed by treatment of 2‐bromoisobutylate immobilized in the side chain of NwPS with Sm (II) iodide. By using this NwPS‐bound initiator, polymerization of a series of methacrylates (=solid‐supported polymerization) was studied to find its two aspects: (1) In the early stages, the rate constant for each methacrylate was comparable to that for its conventional solution‐phase polymerization using a Sm (III) enolate, suggesting that methacrylate can be efficiently supplied to the propagating end by its free permeation without any interference by the networked structure of the matrix. (2) After the early stages, the rate constant decreased remarkably, implying that permeation of methacrylate was sterically interfered by the formed poly(methacrylate) that filled the confined space in NwPS, as supported by a SEM image of the resulting beads, of which pores were filled with the formed polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1510–1521, 2009 相似文献
168.
Vapor–liquid equilibria and saturated density for carbon dioxide + tetrahydrofuran mixtures at high pressures were measured by the analytical method at the temperatures 298.15 and 313.15 K. The experimental apparatus equipped with three Anton Paar DMA 512S vibrating tube density meters was previously developed for measuring vapor–liquid–liquid equilibrium at high pressures. The equilibrium composition and saturated density of each phase were determined by gas chromatograph and vibrating tube density meters, respectively. The bubble point pressure at the temperature 313.15 K was further measured by the synthetic method. The experimental data were correlated with Soave–Redlich–Kwong (SRK) equation of state and the pseudocubic equation of state. 相似文献
169.
Yoshimi Sueishi Atsushi Miyata Daisuke Yoshioka Masato Kamibayashi Yashige Kotake 《Journal of inclusion phenomena and macrocyclic chemistry》2010,66(3-4):357-364
The effect of CD-inclusion on spin-trapping rates and spin-adduct decay rates for sulfur trioxide radical anion (SO3 ??) was investigated. SO3 ?? radical was produced with UV photolysis of sodium sulfite in basic aqueous solution, and spin-trapped with various spin traps, i.e., PBN (α-phenyl-N-t-butylnitrone), DMPO (5,5-dimethyl pyrroline-1-oxide), and three other phosphoryl DMPO-type spin traps. A modified β-CD, 6-O-α-d-glucosyl-β-cyclodextrin (G-β-CD) having better inclusion properties than β-CD, was employed. Upon adding excess G-β-CD, decay rates of SO3 ?? radical adducts significantly decreased in most spin traps. Half-lives of SO3 ?? radical adducts of phosphoryl spin traps were one to two orders of magnitude longer than that of PBN or DMPO, and the G-β-CD addition further extended the half-life time. The spin traps containing phosphoryl-group all showed higher SO3 ?? trapping rates than those of PBN and DMPO, but two phosphoryl spin traps achieved slower trapping rates by G-β-CD addition. In addition, the structures of CD-inclusion complexes of spin traps were established by means of 1D and 2D NMR measurements. Based on the results, the influences of inclusion on the spin-trapping rate processes and spin-adduct stabilizations were discussed. We conclude that substituents in DMPO-type spin traps may be modified to provide best spin-trapping capabilities in the presence or absence of CD. 相似文献
170.
Hiroyuki Suga Satoshi Higuchi Daisuke Ishimoto Yuta Hashimoto Teruko Tsuchida Toshihide Baba 《Tetrahedron》2010,66(16):3070-6287
High enantioselectivities (94-96% ee) were obtained for the inverse electron-demand 1,3-dipolar cycloadditions between cyclohexyl vinyl ether and 2-benzopyrylium-4-olate generated via Rh2(OAc)4-catalyzed decomposition of o-methoxycarbonyl-α-diazoacetophenone. The reactions were effectively catalyzed by Eu(OTf)3, Ho(OTf)3, or Gd(OTf)3 complexes (10 mol %) of chiral 2,6-bis[(4S,5S)-4,5-diphenyl-2-oxazolinyl]pyridine. The reactions with the other electron-rich dipolarophiles such as allyl alcohol, 2,3-dihydrofuran, and butyl-tert-butyldimethylsilylketene acetal showed moderate enanantioselectivities (60-73% ee). Good to high enantioselectivities (73-97% ee) were also obtained for the cycloadditions between 3-acyl-2-benzopyrylium-4-olates, generated from methyl 2-(2-diazo-1,3-dioxoalkyl)benzoates and butyl or cyclohexyl vinyl ethers, in the presence of binaphthyldiimine (BINIM)-Ni(II) complexes (10 mol %). Under similar conditions, the reaction between methyl 2-(2-diazo-1,3-dioxohexyl)benzoate and 2,3-dihydrofuran was highly endo-selective, and moderately enantioselective (70% ee). For the BINIM-Ni(II)-catalyzed reactions of cyclohexyl vinyl ether, the use of an epoxyindanone as the 3-acyl-2-benzopyrylium-4-olate precursor revealed that the chiral Lewis acid can function as a catalyst for asymmetric induction. The scope of the cyclic carbonyl ylides was extended to those generated from 1-diazo-2,5-pentanedione derivatives, which were reacted with butyl or TBS vinyl ether and catalyzed using the (4S,5S)-Pybox-4,5-Ph2-Lu(OTf)3 complex to give good levels of asymmetric inductions (75-84% ee). 相似文献