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41.
Nucleophilic reactions with Grignard reagents and the Mukaiyama aldol reactions of the naphthaldehydes having the (2,4, 6-triisopropylphenyl)sulfinyl group produced products with high stereoselectivity. In these reactions, the stereochemistry of the major products changes depending on the Lewis acids used. Reduction of the 2-acyl-1-[(2,4,6-triisopropylphenyl)sulfinyl]naphthalenes also proceeds with high stereoselectivity but with a different stereochemistry depending on the reducing agents. We have demonstrated, by the mechanistic consideration based on the X-ray crystal structures as well as the (1)H and (13)C NMR spectral data, that the extremely high and specific stereoselectivities of these reactions are due to the predominant rotamer around the C(naph)-S axis. Synthesis of enantiomerically pure 2-naphthylmethanol is provided as an example. 相似文献
42.
Tan L Yasuda N Yoshikawa N Hartner FW Eng KK Leonard WR Tsay FR Volante RP Tillyer RD 《The Journal of organic chemistry》2005,70(20):8027-8034
[Chemical reaction: See text] A Et3Al mediated intramolecular epoxide opening, cyclopropanation reaction is described. The transformation provided highly functionalized bicyclo[3.1.0]hexane systems in high efficiency and with perfect H or F endo selectivity. Application of this reaction to the synthesis of mGluR2/3 agonist 1 (43% overall yield) and a few intermediates suitable for the synthesis of other bicyclo[3.1.0]hexane mGluR2/3 agonists is discussed. 相似文献
43.
Tsutomu Shiragami Katsunori Tanaka Yoshito Andou Shin-ichiro Tsunami Jin Matsumoto Hongxia Luo Yasuyuki Araki Osamu Ito Haruo Inoue Masahide Yasuda 《Journal of photochemistry and photobiology. A, Chemistry》2005,170(3):287-297
Tetraphenylporphyrinatoantimony(V) complexes, linked to boron-dipyrrin chromophores on axial ligands, were synthesized. The fluorescence spectra of 1a, 1b and 1c (3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1a); 6-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]hexyloxo(methoxo)antimony(V) tetraphenylporphyrin bromide (1b); bis{3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo}antimony(V) tetraphenylporphyrin bromide (1c)) were analyzed under the excitations of N,N′-difluorobornyl-5-dipyrrinylphenyl (Bdpy) and tetraphenylporphyrinatoantimony(V) (Sb(TPP)) chromophores. Under the irradiation of Bdpy chromophore, the excitation energy was transferred from Bdpy chromophore to the Sb(TPP) moiety at 0.13–0.40 of the quantum yields, even in a polar solvent. On the other hand, the emission of Sb(TPP) chromophores was quenched by Bdpy chromophores at rate constants of 108–109 s−1, independent of on the solvent polarity. Under the excitation of the Bdpy chromophore of 1d (3-[4-(N,N′-difluorobornyl-5-dipyrrinyl)phenyl]propoxo(phenyloxo)antimony(V) tetraphenylporphyrin bromide) involving both the Bdpy and the phenoxy chromophores on the axial ligands, the excited singlet state of the Sb(TPP) chromophore generated by the energy transfer from the Bdpy chromophore was quenched by the phenoxy ligand via non-radiative processes involving electron transfer. However, rapid back electron-transfer may occur because no absorption of the anion radical of Sb(TPP) was observed by nanosecond laser photolysis. 相似文献
44.
45.
Y. Saito-Kokubu K. Yasuda M. Magara Y. Miyamoto S. Sakurai S. Usuda H. Yamazaki S. Yoshikawa 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(1):183-186
In order to know the distribution of plutonium derived from the Nagasaki atomic bomb, soil samples were measured to determine
the 240Pu/239Pu isotope ratio of and concentrations of 239+240Pu and 137Cs. The 239+240Pu concentrations in soils, except for Nishiyama area, were close to the average concentration of soil collected in Japan.
In soils collected at the Nishiyama area and at the eastern area of Nagasaki Prefecture and at part of northern area in Kumamoto
Prefecture, the 240Pu/239Pu ratios were lower than the global fallout values. This suggests that plutonium from the atomic bomb was deposited in the
eastern area from the hypocenter reaching up to 100 km eastwards. 相似文献
46.
The objective of this study was to examine some fundamental factors involved in the design and construction of the anode magnetron dc glow discharge processes as well as its performance in plasma cleaning and polymerization. Those advantages of anode magnetron include the capability of the magnetron to operate at low pressure, as well as decreasing the thickness of cathode dark space, i.e., the negative glow which contains a higher concentration of ions and active species was more closely to the cathode surface, which makes the plasma surface cleaning and polymerization an effective and uniform processes. The deposition rate at a given discharge power is increased by the presence of anode magnetrons, and is also much higher relative to rf and af. The refractive index of dc plasma film at a given polymer thickness (such as TMS, 70 nm, RI: 2.4) is higher than rf, af, and cascade arc plasma (RI: 1.6–1.7). 相似文献
47.
Miyoji Hanaoka Shingo Yasuda Kazuyoshi Nagami Keiko Okajima Takeshi Imanishi 《Tetrahedron letters》1979,20(39):3749-3752
Irradiation of the berberinephenolbetaines (, , and ) effected valence tautomerization to give the 8,14-cycloberbines (, , and ), the aziridine derivatives, in high yield. The 8,14-cycloberbines were efficiently converted to the spirobenzylisoquinolines by regioselective C bond cleavage. 相似文献
48.
Reaction modes of n-butylmagnesium bromide with α,β-unsaturated esters, ketones, and nitriles were investigated in ether under anionic polymerization conditions. n-Butane and conjugate addition products observed were with all the monomers examined, but carbonyl addition products were not detected except with the unsaturated esters. Product distribution depends mainly upon reaction temperature and the concentration of the Grignard reagent, not upon the concentration of the unsaturated compounds. n-Butyl-magnesium bromide etherate in toluene gave similar results. 相似文献
49.
Hideki Misaka Eisuke Tamura Kosuke Makiguchi Kensuke Kamoshida Ryosuke Sakai Toshifumi Satoh Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2012,50(10):1941-1952
For the living ring‐opening polymerization (ROP) of epoxy monomers, the catalytic activity of organic superbases, tert‐butylimino‐tris(dimethylamino)phosphorane, 1‐tert‐butyl‐2,2,4,4,4‐pentakis(dimethylamino)‐2Λ5,4Λ5‐catenadi(phosphazene), 2,8,9‐triisobutyl‐2,5,8,9‐tetraaza‐1‐phosphabicyclo[3.3.3]undecane, and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris(dimethylamino)phosphoranylidenamino]‐2Λ5,4Λ5‐catenadi(phosphazene) (t‐Bu‐P4), was confirmed. Among these superbases, only t‐Bu‐P4 showed catalytic activity for the ROP of 1,2‐butylene oxide (BO) to afford poly(1,2‐butylene oxide) (PBO) with predicted molecular weight and narrow molecular weight distribution. The results of the kinetic, post‐polymerization experiments, and MALDI‐TOF MS measurement revealed that the t‐Bu‐P4‐catalyzed ROP of BO proceeded in a living manner in which the alcohol acted as the initiator. This alcohol/t‐Bu‐P4 system was applicable to the glycidol derivatives, such as benzyl glycidyl ether (BnGE) and t‐butyl glycidyl ether, to afford well‐defined protected polyglycidols. The α‐functionalized polyethers could be obtained using different functionalized initiators, such as 4‐vinylbenzyl alcohol, 5‐hexen‐1‐ol, and 6‐azide‐1‐hexanol. In addition, the well‐defined cyclic‐PBO and PBnGE were successfully synthesized using the combination of t‐Bu‐P4‐catalyzed ROP and click cyclization. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
50.