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141.
Bang JK Naka H Teruya K Aimoto S Konno H Nosaka K Tatsumi T Akaji K 《The Journal of organic chemistry》2005,70(25):10596-10599
[reaction: see text] The solid-phase Horner-Emmons reaction was successfully applied for the convenient syntheses of olefin-containing protease inhibitors. The isomerization during the solid-phase Horner-Emmons reaction can be minimized simply by the use of an appropriate amount of the base. The synthesized olefin peptides, which have an olefin gamma-amino acid at the scissile site, were found to act as effective inhibitors for the HTLV-1 protease for the first time. 相似文献
142.
Shuzo Takeda Masao Chino Masatoshi Kiuchi Kunitomo Adachi 《Tetrahedron letters》2005,46(31):5169-5172
A novel method for selective and direct phosphorylation of various 1,3-diols using silver(I) oxide, tetrabenzyl pyrophosphate (TBPP), and tetrahexylammonium iodide affording mono-phosphates was developed. We applied the present method to the synthesis of FTY720-phosphate. 相似文献
143.
Mitsunori Honda Yuichi Yamamoto Hideki Tsuchida Masahito Segi Tadashi Nakajima 《Tetrahedron letters》2005,46(38):6465-6468
Treatment of cyclopropylsilylmethanols derived from cyclopropyl silyl ketones with acid catalyst gives the corresponding silyl-substituted homoallyl derivatives in high yields with good stereoselectivity, independent of the substituents on the cyclopropyl ring. Cyclopropylsilylmethanols having a n-, s-butyl or phenyl group on the carbinyl carbon react to afford the E-homoallyl derivatives selectively. On the other hand, the reaction of cyclopropylsilylmethanols having a tert-butyl group gives Z-isomers exclusively. The following protiodesilylation of the resulting homoallyl derivatives proceeds with retention of configuration. 相似文献
144.
Satoru Amou Shin Nishimura Akio Takahashi Tokio Hagiwara Hiroshi Hamana Tadashi Narita 《Journal of polymer science. Part A, Polymer chemistry》1999,37(3):341-347
N‐(4‐Tetrahydropyranyl‐oxy‐phenyl)maleimide (THPMI) was prepared and polymerized by radical or anionic initiators. THPMI could be polymerized by 2,2′‐azobis(isobutyronitrile) (AIBN) and potassium tert‐butoxide. Radical polymers (poly(THPMI)r) were obtained in 15–50% yields for AIBN in THF at 65°C after 2–5 h. The yield of anionic polymers (poly(THPMI)a) obtained from potassium tert‐butoxide in THF at 0°C after 20 h was 91%. The molecular weights of poly(THPMI)r and poly(THPMI)a were Mn = 2750–3300 (Mw/Mn = 1.2–3.3) and Mn = 11300 (Mw/Mn = 6.0), respectively. The difference in molecular weights of the polymers was due to the differences in the termination mechanism of polymerization and the solubility of these polymers in THF. The thermal decomposition temperatures were 205 and 365°C. The first decomposition step was based on elimination of the tetrahydropyranyl group from the poly(THPMI). Positive image patterns were obtained by chemical amplification of positive photoresist composed of poly(THPMI) and 4‐morpholinophenyl diazonium trifluoromethanesulfonate used as an acid generator. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 341–347, 1999 相似文献
145.
Yokoyama K Kudo F Kuwahara M Inomata K Tamegai H Eguchi T Kakinuma K 《Journal of the American Chemical Society》2005,127(16):5869-5874
The doubly functional aminotransferase BtrS in the 2-deoxystreptamine (DOS) biosynthesis, in which two transaminations are involved, was characterized by a genetic as well as a chemical approach with the heterologously expressed enzyme. The gene disruption study clearly showed that BtrS is involved, in addition to the previously confirmed first transamination, in the second transamination as well. This dual function of BtrS for the DOS biosynthesis was further confirmed by the structural determination of the reverse reaction product from DOS. Enantiospecific formation of the reverse reaction product from DOS clearly showed that BtrS distinguishes the enantiotopic amino groups of DOS, but in contrast, both enantiomers of 2-deoxy-scyllo-inosose (DOI) were efficiently accepted by BtrS to give a racemic product. This unique stereochemical recognition of DOI chirality and DOS prochirality by BtrS is mechanistically explained by a specific hydrogen-bond donating force in the enzyme active site as a particular feature of this doubly functional enzyme. 相似文献
146.
Kawasaki H Sasaki A Kawashima T Sasaki S Kakehashi R Yamashita I Fukada K Kato T Maeda H 《Langmuir : the ACS journal of surfaces and colloids》2005,21(13):5731-5737
Lyotropic phase behavior of the nonionic and the half-ionized oleyldimethylamine oxide (OlDMAO)/water systems was investigated using polarized light microscopy, small-angle X-ray diffraction, and differential scanning calorimetry. Nonionic OlDMAO formed isotropic micellar solution, nematic, hexagonal, cubic, and lamellar liquid crystalline phases as the surfactant concentration increased. In contrast, half-ionized OlDMAO (i.e., 1:1 mixture of the nonionic and the protonated species) had a greater tendency to form bilayer structures, and the phase diagram became quite similar to those of double-chained ionic surfactants rather than single-chained ones, despite the introduction of positive charges to the nonionic one. The preference of the bilayer structures in the half-ionized OlDMAO was interpreted in terms of the dimers stabilized by the hydrogen bond between the nonionic and protonated species. For alkyldimethylamine oxides with a saturated hydrocarbon chain (CnDMAO, chain length: n = 14, 16, and 18), the phase sequence of lyotropic liquid crystals was hardly affected by the protonation, but an elongation of the cylinders of the hexagonal phase was observed for the half-ionized C14DMAO. Consequently, it can be considered that the dominant bilayer formation of the half-ionized OlDMAO is attributed to the combined effect of the hydrogen-bonded dimer formation and the cis-double-bond configuration of the alkyl chain. 相似文献
147.
Ohnishi YY Matsunaga T Nakao Y Sato H Sakaki S 《Journal of the American Chemical Society》2005,127(11):4021-4032
Ruthenium-catalyzed hydrogenation of carbon dioxide to formic acid was theoretically investigated with DFT and MP4(SDQ) methods, where a real catalyst, cis-Ru(H)2(PMe3)3, was employed in calculations and compared with a model catalyst, cis-Ru(H)2(PH3)3. Significant differences between the real and model systems are observed in CO2 insertion into the Ru(II)-H bond, isomerization of a ruthenium(II) eta1-formate intermediate, and metathesis of the eta1-formate intermediate with a dihydrogen molecule. All these reactions more easily occur in the real system than in the model system. The differences are interpreted in terms that PMe3 is more donating than PH3 and the trans-influence of PMe3 is stronger than that of PH3. The rate-determining step is the CO2 insertion into the Ru(II)-H bond. Its deltaG(o++) value is 16.8 (6.8) kcal/mol, where the value without parentheses is calculated with the MP4(SDQ) method and that in parentheses is calculated with the DFT method. Because this insertion is considerably endothermic, the coordination of the dihydrogen molecule with the ruthenium(II)-eta1-formate intermediate must necessarily occur to suppress the deinsertion. This means that the reaction rate increases with increase in the pressure of dihydrogen molecule, which is consistent with the experimental results. Solvent effects were investigated with the DPCM method. The activation barrier and reaction energy of the CO2 insertion reaction moderately decrease in the order gas phase > n-heptane > THF, while the activation barrier of the metathesis considerably increases in the order gas phase < n-heptane < THF. Thus, a polar solvent should be used because the insertion reaction is the rate-determining step. 相似文献
148.
We demonstrated the deposition of nanometric Zn dots using photodissociation with gas-phase diethylzinc and an optical near field under nonresonant conditions. To explain the experimental results, we proposed an exciton-phonon polariton model, and discuss the quantitative experimental dependence of the deposition rate on the optical power and photon energy based on photodissociation involving multiple-step excitation via molecular vibration modes. The physical basis of this process, which seems to violate the Franck-Condon principle, is the optically nonadiabatic excitation of the molecular vibration mode due to the steep spatial gradient of the optical near-field energy. 相似文献
149.
We describe an efficient synthesis of 2,6- and 2,3-sialyl T antigens linked to serine in a one-pot glycosylation. We first investigated the glycosidation of thiosialosides by varying the N-protecting group. Modification of the C-5 amino group of beta-thiosialosides into the N-9-fluorenylmethoxycarbonyl, N-2,2,2-trichloroethoxycarbonyl (N-Troc), and N-trichloroacetyl derivatives enhanced the reactivity of these compounds towards glycosidation. Addition of a minimum amount of 3 A molecular sieves was also effective in improving the yield of alpha-linked sialosides. Next, we conducted one-pot syntheses of the glycosyl amino acids by using the N-Troc sialyl donor. The N-Troc derivative can be converted into the N-acetyl derivative without racemization of the amino acids. Branched-type one-pot glycosylation, initiated by regioselective glycosylation of the 3,6-dihydroxy galactoside with the N-Troc-beta-thiophenyl sialoside, provided the protected 2,6-sialyl T antigen in good yield. Linear-type one-pot glycosylation, initiated by chemoselective glycosylation of galactosyl fluoride with the N-Troc-beta-thiophenyl sialoside, afforded the protected 2,3-sialyl T antigen in excellent yield. Both protected glycosyl amino acids were converted into the fully deprotected 2,6- and 2,3-sialyl T antigens linked to serine in good yields. 相似文献
150.
Umetsu K Tanaka M Yuasa I Adachi N Miyoshi A Kashimura S Park KS Wei YH Watanabe G Osawa M 《Electrophoresis》2005,26(1):91-98
We present a reliable, rapid, and economical multiplex amplified product-length polymorphism (APLP) method for analyzing the haplogroup-diagnostic mitochondrial single-nucleotide polymorphisms (mtSNPs) in East Asian populations. By examining only 36 haplogroup-specific mtSNPs in the coding region by using four 9-multiplex polymerase chain reaction (PCR) and subsequent electrophoresis, we could safely assign 1815 individuals from 8 populations of Japanese, Korean, Chinese, and Germans to 45 relevant haplogroups. This multiplex APLP analysis of coding-region mtSNPs for haplogrouping is especially useful not only for molecular phylogenetic studies but also for large-scale association studies due to its rapid and economical nature. This is the first panel of mtSNPs in the coding region to be used for haplogrouping of East Asian populations. 相似文献