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71.
A new route for (2S,3S,4S)-form, the physiologically active stereoisomer of dehydroxymethylepoxyquinomicin (DHMEQ), a potent NF-κB inhibitor, was established by chemoenzymatic approach. Elaboration on the asymmetric epoxidation of a p-benzoquinone monoketal with benzylcinchonidinium tert-butylhydroperoxide yielded an epoxyenone, in 79.8% ee and 57% yield in reproducible manner. By way of the transformation of this key intermediate to enantiomerically pure (2S,3S,4S)-DHMEQ, the contaminating undesired enantiomer could be effectively removed by applying Burkholderia cepacia lipase-catalyzed hydrolysis of diacylated precursor. The above integrated combination of chemical asymmetric synthesis and enzyme-catalyzed kinetic resolution enabled us to prepare active DHMEQ in a large-scale. 相似文献
72.
Ni-catalyzed hydrosilylative cyclization of difluoro-substituted 1,6-enynes can be carried out. The presence of a geminal-difluoromethylene group at an alkene terminus in enynes is essential for the reaction to proceed. 相似文献
73.
A convenient synthesis of chiral 3,3′-disubstituted 1,1′-binaphthyl-2,2′-disulfonic acids (BINSA, 1) was developed. The key was directed ortho-lithiation of BINSA methyl ester 2 with n-BuLi and subsequent reaction with an electrophile. Electrophiles such as Br2, I2, Me3SiOTf, and i-PrOB(Pin) reacted smoothly with 3,3′-dilithiated BINSA methyl ester, and the corresponding 3,3′-dihalo-, 3,3′-bis(trimethylsilyl)-, and 3,3′-diboryl-BINSA derivatives were obtained in yields of 21–78%. This simple synthetic method is highly attractive since the ability to prepare 3,3′-disubstituted BINOLs in advance can be useful. 相似文献
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75.
Jumpei Saito Manabu Tanaka Kenji Miyatake Masahiro Watanabe 《Journal of polymer science. Part A, Polymer chemistry》2010,48(13):2846-2854
A new series of sulfonated polyimide (SPI) copolymers containing NH, OH, or COOH groups were synthesized by the polycondensation of 1,4,5,8‐naphthalnetetracarboxylic dianhydride, 3,3′‐bis(sulfopropoxy)‐4,4′‐diaminobiphenyl, and 3‐(4‐aminophenyl)‐5‐(3‐aminophenyl)‐1H‐1,2,4‐triazole (SPI‐8‐m), 3,5‐bis(4‐aminophenyl)‐1H‐1,2,4‐triazole (SPI‐8‐p), 3,6‐diaminocarbazole (SPI‐9), 3,5‐diamino‐1H‐1,2,4‐triazole (SPI‐10), bis(3‐aminopropyl)‐amine (SPI‐11), 2,6‐diaminopurine (SPI‐12), 2,4‐diamino‐6‐hydroxyprymidine (SPI‐13), or 3,5‐bis(4‐aminophenoxy)benzoic acid (SPI‐14). The obtained SPIs were soluble in polar organic solvents and gave tough and flexible membranes by solution casting. The SPI membranes having NH and COOH groups showed high thermal (decomposition temperature ≈200 °C) and mechanical (maximum stress >22 MPa) stability. Introducing NH groups, especially triazole and carbazole groups, was effective in improving proton conductive properties of SPI membranes at low humidity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2846–2854, 2010 相似文献
76.
197Au and125Te Mössbauer spectroscopy has been applied for the low-temperature β-phases of Ag3AuX2 (X=S, Se, and Te). The values of I. S. and Q. S. for197Au suggest that the gold atoms, linearly coordinated by two chalcogen atoms in these phases, exist as monovalent cations. The125Te Mössbauer spectra suggest that the tellurium atoms are substantially ionic for both Ag2Te and Ag3AuTe2. The nature of X-Au-X bonds is discussed on the basis of the Mössbauer data and the bond distances. 相似文献
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The aim of the present paper is to show that the convergence rate of the parametric cubic spline approximation of a plane curve is of order four instead of order three. For the first and second derivatives, the rates are of order three and two, respectively. Finally some numerical examples are given to illustrate the predicted error behaviour. 相似文献
80.
Manabu Kiguchi Tatsuya Konishi Shinichi Miura Kei Murakoshi 《Physica E: Low-dimensional Systems and Nanostructures》2005,29(3-4):530
We have mechanically fabricated Ni and Cu nano-constrictions in solution to study their quantized conductance behavior under electrochemical potential control. Conductance quantization was observed at both metals in solution at room temperature for the first time. The conductance of Cu nano-constriction was quantized in units of G0(=2e2/h). A sharp 1G0 peak was observed in the conductance histogram. For Ni, a rather broad peak at 1–1.5G0 was observed in the histogram. The conductance quantization behavior was discussed by comparing previously documented results of nano-constrictions fabricated in air or ultra-high vacuum conditions, with those fabricated in solution. 相似文献