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961.
Mikami K Wakabayashi K Yusa Y Aikawa K 《Chemical communications (Cambridge, England)》2006,(22):2365-2367
The chirality of an achiral benzophenone-based rhodium complex can be controlled by chiral diamines to afford significantly high enantioselectivity in the catalytic asymmetric transfer hydrogenation of ketones (up to 99% ee, 99% yield). 相似文献
962.
Shoji M Akiyama N Tsubone K Lash LL Sanders JM Swanson GT Sakai R Shimamoto K Oikawa M Sasaki M 《The Journal of organic chemistry》2006,71(14):5208-5220
Dysiherbaine (1) and its congener neodysiherbaine A (2) are naturally occurring excitatory amino acids with selective and potent agonistic activity for ionotropic glutamate receptors. We describe herein the total synthesis of 2 and its structural analogues 3-8. Advanced key intermediate 16 was employed as a branching point to assemble a series of these analogues 3-8 with respect to the C8 and C9 functionalities, which would not have been accessible through manipulations of the natural product itself. The synthesis of key intermediate 16 features (i) stereocontrolled C-glycosylation to set the C6 stereocenter, (ii) concise synthesis of the bicyclic ether skeleton through chemo- and stereoselective dihydroxylation of the exo-olefin and stereoselective epoxidation of the endo-olefin, followed by epoxide ring opening/5-exo ring closure, and (iii) catalytic asymmetric hydrogenation of enamide ester to construct the amino acid appendage. A preliminary biological evaluation of analogues for their in vivo toxicity against mice and binding affinity for glutamate receptors showed that both the type and stereochemistry of the C8 and C9 functional groups affected the subtype selectivity of dysiherbaine analogues for members of the kainic acid receptor family. 相似文献
963.
Koichi Mitsudo 《Tetrahedron letters》2006,47(29):5147-5150
N-Glycosylation of 2,3-dideoxy-1-[(2-pyridylmethyl)thio]glycosides (1a) using several activators is described. NBS-promoted glycosylation reaction utilizing either the α- or β-thiodideoxyglycoside proceeded smoothly at −78 °C to give the corresponding dideoxynucleoside in a β-selective manner, presumably through a common glycosyl donor. 相似文献
964.
We investigate the cosmological moduli problem by studying a modulus decay in detail and find that the branching ratio of the gravitino production is generically of O(0.01-1), which causes another cosmological disaster. Consequently, the cosmological moduli problem cannot be solved simply by making the modulus mass heavier than 100 TeV. We also illustrate our results by explicitly calculating the branching ratio into the gravitinos in the mixed modulus-anomaly model. 相似文献
965.
The first total synthesis of (-)-sordarin (1) was accomplished exploiting the following key reactions: (i) Ag(I)-catalyzed oxidative radical cyclization of a cyclopropanol derivative leading to a bicyclo[5.3.0]decan-3-one skeleton; (ii) Pd(0)-catalyzed intramolecular allylation reaction resulting in the entire strained bicyclo[2.2.1]heptan-2-one framework of sordaricin (2); (iii) selective dihydroxylation of terminal alkenes by the combined use of OsO(4) and PhB(OH)(2); and (iv) beta(1,2-cis)-selective glycosidation via a 1,3-anchimeric assistance from a 4-methoxybenzoyl group. 相似文献
966.
Application of the HPLC hyphenated techniques of LC-MS, LC-NMR and solvent-elimination LC-IR was demonstrated by the identification of the degradation products of a third generation cephalosporin antibiotic, cefpodoxime proxetil, in solid state, drug formulation and solution. Molecular weight and fragment information were obtained by LC-MS, and detailed structural information was confirmed by LC-NMR. Information on the carboxyl functional group obtained by solvent-elimination LC-IR was useful for confirmation of the ester hydrolysis. The degradation products were successfully identified without complicated isolation or purification processes. 相似文献
967.
Kitagawa T Idomoto Y Matsubara H Hobara D Kakiuchi T Okazaki T Komatsu K 《The Journal of organic chemistry》2006,71(4):1362-1369
Tripod-shaped trithiols 1-3, containing CH2SH groups at the three bridgehead positions of the adamantane framework and a halogen-containing group [Br (1), p-BrC6H4 (2), or p-IC6H4 (3)] at the fourth bridgehead, were synthesized, and self-assembled monolayers (SAMs) were prepared on atomically flat Au111 surfaces. The three-point chemisorption of these tripods was confirmed by polarization modulation infrared reflection absorption spectroscopy, which showed the absence of a S-H stretching band. Scanning tunneling microscopy of the SAM of 1 exhibited a hexagonal arrangement of the adsorbed molecule with a lattice constant of 8.7 angstroms. A unidirectionally oriented, head-to-tail array of 1, which allows the close approach of neighboring molecules, is proposed as a reasonable model of the two-dimensional crystal, where the adsorbed sulfur atoms form a quasi-(radical3 x radical3)R30 degrees lattice. The charge of the electrochemical reductive desorption of the SAM of 1 was in good agreement with the expected surface coverage, while the SAMs of 2 and 3 showed somewhat less (ca. 70%) charge. The large negative reduction peak potentials, observed for the SAM of 1, are taken to indicate a tight anchoring of this tripod by three sulfur atoms. 相似文献
968.
Fukutsu N Sakamaki Y Kawasaki T Saito K Nakazawa H 《Chemical & pharmaceutical bulletin》2006,54(10):1469-1472
Cross-contamination is a critical issue for pharmaceutical manufacturing, especially for beta-lactam antibiotics. Thus, an analytical method for the simultaneous determination of beta-lactam antibiotics cefmetazole (CMZ) and cefpodoxime proxetil (CPDXPR) contaminants in non-beta-lactam pharmaceuticals was developed using high-performance liquid chromatography-tandem mass spectrometry. The developed method was found to be sensitive at the detection limit of 0.002 ppm for both compounds. Mean recoveries of CMZ and CPDXPR from olmesartan medoxomil (OLM) tablets were 96.7 to 102.2% and 88.9 to 94.2%, respectively. The developed method was successfully applied for the verification of CMZ and CPDXPR contamination to actually manufactured OLM tablets. 相似文献
969.
Sartori E Ruzzi M Turro NJ Decatur JD Doetschman DC Lawler RG Buchachenko AL Murata Y Komatsu K 《Journal of the American Chemical Society》2006,128(46):14752-14753
The 1H nuclear spin-lattice relaxation time (T1) of H2 and H2@C60 in organic solvents varies with solvent, and it varies proportionally for H2 and for H2@C60. Since intermolecular magnetic interactions are ruled out, the solvent must influence the modulating processes of the relaxation mechanisms of H2 both in the solvent cage and inside C60. The temperature dependence of T1 also is very similar for H2 and H2@C60, T1 going through a maximum by varying the temperature in solvents which allow a wide range of temperatures to be explored. This behavior is attributed to the presence of dipolar and spin-rotation mechanisms which have an opposite dependence on temperature. 相似文献
970.
Inamura S Fujimoto Y Kawasaki A Shiokawa Z Woelk E Heine H Lindner B Inohara N Kusumoto S Fukase K 《Organic & biomolecular chemistry》2006,4(2):232-242
The peptidoglycan (PG) bacterial cell wall glycoconjugate has been well known as a strong immunopotentiator. Partial structures of PG were chemically synthesized for elucidation of precise biological activities. Effective construction of distinct repeating glycans of PG was accomplished by the coupling of a key disaccharide glucosaminyl-beta(1-4)-muramic acid unit. Stereoselective glycosylation of disaccharide units was achieved by neighboring group participation of the N-Troc (Troc = 2,2,2-trichloroethoxycarbonyl) group and appropriate reactivity of N-Troc-glucosaminyl trichloroacetimidate. By using an efficient synthetic strategy, mono-, di-, tetra- and octasaccharide fragments of PG were synthesized in high yields. The biological activity of synthetic fragments of PG was evaluated by induction of tumor necrosis factor-alpha (TNF-alpha) from human monocytes, and toll-like receptor 2 (TLR2) and Nod2 dependencies by using transfected HEK293 cells, respectively. Here we reveal that TLR2 was not stimulated by the series of synthetic PG partial structures, whereas Nod2 recognizes the partial structures containing the MDP moiety. 相似文献