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71.
The oxidation of primary, secondary, allylic, benzylic, hindered and bicyclic alcohols with dimethyl sulfoxide (DMSO) “activated” by numerous electrophiles was studied: yields of carbonyls, by-products and recovered alcohols were quantitatively determined. Pathways for carbonyl and by-product formation are presented. Generally, yields of carbonyls increase with increased steric hindrance in the alcohols. Steric effects of tertiary amines, used for basification, were also investigated, and the results are consistent with the suggested reaction pathways. Among previously unreported “activators,” oxalyl chloride is the most generally effective; yields of carbonyls are typically over 95%. Thionyl chloride is also a satisfactory “activator” although yields of carbonyls are not quite as high. An improved method of preparation of alkyl methylthiomethyl ethers, by-products of the oxidation process, is reported. 相似文献
72.
Rao FV Houston DR Boot RG Aerts JM Hodkinson M Adams DJ Shiomi K Omura S van Aalten DM 《Chemistry & biology》2005,12(1):65-76
Family 18 chitinases play key roles in organisms ranging from bacteria to man. There is a need for specific, potent inhibitors to probe the function of these chitinases in different organisms. Such molecules could also provide leads for the development of chemotherapeuticals with fungicidal, insecticidal, or anti-inflammatory potential. Recently, two natural product peptides, argifin and argadin, have been characterized, which structurally mimic chitinase-chitooligosaccharide interactions and inhibit a bacterial chitinase in the nM-mM range. Here, we show that these inhibitors also act on human and Aspergillus fumigatus chitinases. The structures of these enzymes in complex with argifin and argadin, together with mutagenesis, fluorescence, and enzymology, reveal that subtle changes in the binding site dramatically affect affinity and selectivity. The data show that it may be possible to develop specific chitinase inhibitors based on the argifin/argadin scaffolds. 相似文献
73.
Kurimoto A Tobe M Ogita H Ogino T Takaku H Ichii S Kawakami H Isobe Y 《Chemical & pharmaceutical bulletin》2004,52(4):466-469
In order to improve the oral bioavailability of 9-benzyl-8-hydroxy-2-(2-hydroxyethylthio)adenine (SM-295072), a potent interferon (IFN) inducing agent, we synthesized prodrugs of it by utilizing the hydroxy groups at the C(2)-side chain and/or the C(8)-position. The carbonate prodrug at the C(8)-position was more effective than that at the C(2)-side chain for oral absorption in rats. Among the compounds prepared, compound 6 demonstrated the most preferable prodrug properties, and the maximum plasma concentration of 6 was approximately 4-fold higher than that of SM-295072. Furthermore, compound 6 was dose-dependently absorbed in monkeys by oral administration, and exhibited a potent IFN-inducting activity that correlated well with its plasma drug concentration. 相似文献
74.
Sunazuka T Shirahata T Tsuchiya S Hirose T Mori R Harigaya Y Kuwajima I Omura S 《Organic letters》2005,7(5):941-943
The stereoselective synthesis of tetracyclic intermediate, the indoline spiroaminal 3 for neoxaline (1) and oxaline (2), has been accomplished. The key step of the stereoselective synthesis of 3 was the Lewis acid mediated transcyclization of 4 to the diaminal 18, and the tungstate-catalyzed oxidation of 18 to obtain the nitrone 19, which easily cyclizes to the indoline spiroaminal framework 3. [structure: see text] 相似文献
75.
Tadao Kondo Keiji Yamamoto Takashi Omura Makoto Kumada 《Journal of organometallic chemistry》1973,60(2):287-301
Nine ferrocenylmethyl derivatives of silicon and germanium were prepared and found to undergo methanolysis of their C---M (M = Si or Ge) bonds in the presence of ferric ions to give ferrocenylmethyl methyl ether. For this reaction, relative rate studies and polarographic studies of the pertinent ferrocene derivatives were carried out to obtain some insight into the reaction mechanism. The substituted ferricenium ion intermediate which is formed by oxidation with ferric ions can readily undergo nucleophilic attack by methanol on the metal (Si or Ge) atom. The observed higher reactivity of the germanium derivative relative to the silicon congener in this reaction is not that expected for the usual base-catalyzed attack at the metal atom, and may be reasonably interpreted in terms of a possible change in the transition state depending on the nature of the leaving group, viz. on the acidity of the corresponding hydrocarbon acid, in the solvolysis of the C---M bond. 相似文献
76.
Hirose T Sunazuka T Tsuchiya S Tanaka T Kojima Y Mori R Iwatsuki M Omura S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(27):8220-8238
This article describes the determination of the absolute configurations of the guadinomines, which are novel cyclic guanidyl natural products that are inhibitors of the type III secretion system (TTSS) of bacteria. Any compound that interrupts the TTSS of bacteria is potentially an ideal anti-infectious drug. The reliable asymmetric synthesis of guadinomines has revealed their absolute configurations, which could not have been defined without this synthetic approach. Our report not only describes the asymmetric total synthesis of the title compounds, but also demonstrates the novel concise synthesis of tri-substituted piperazinone cores as optically pure forms. The novel feature of our method is an intramolecular S(N)2 cyclization that uses PPh(3) and I(2) to construct the unique 5-membered cyclic guanidine substructure. 相似文献
77.
78.
79.
The effects of higher-energy photon from 123I (p, 5n) on the SPECT image quality were evaluated. The quality was evaluated by image contrast and %rms. Image contrast had similar tendency to planar and SPECT FWHM value. %rms was affected by septal penetration. Using 140 keV high resolution collimator (140 keV HR), image contrast was superior to that for 300 keV medium energy collimator (300 keV ME), but septal penetration rate (SPR) was 18% and %rms was 10.5. When quantitation is required, the collimator with less SPR than 18% is recommended for SPECT imaging. Using 300 keV ME, SPR was 0.05%, but spatial resolution and image contrast were inferior to that for 140 keV HR. 相似文献
80.
Volatility, which represents the magnitude of fluctuating asset prices or returns, is used in the problems of finance to design optimal asset allocations and to calculate the price of derivatives. Since volatility is unobservable, it is identified and estimated by latent variable models known as volatility fluctuation models. Almost all conventional volatility fluctuation models are linear time-series models and thus are difficult to capture nonlinear and/or non-Gaussian properties of volatility dynamics. In this study, we propose an entropy based Student’s t-process Dynamical model (ETPDM) as a volatility fluctuation model combined with both nonlinear dynamics and non-Gaussian noise. The ETPDM estimates its latent variables and intrinsic parameters by a robust particle filtering based on a generalized H-theorem for a relative entropy. To test the performance of the ETPDM, we implement numerical experiments for financial time-series and confirm the robustness for a small number of particles by comparing with the conventional particle filtering. 相似文献