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41.
(+)-Biotin (1) was synthesized in 25% overall yield over 11 steps from L-cysteine. The contiguous asymmetric centers at C-3a and C-6a were formed through a novel and highly stereoselective Lewis base-catalyzed cyanosilylation of alpha-amino aldehyde 3 to provide anti-O-TMS-cyanohydrin 4 with high stereoselectivity and in high yield (anti/syn = 92:8, 96%). Treatment of 4 with a di-Grignard reagent, 1,4-bis(bromomagnesio)butane, followed by carbon dioxide, efficiently installed the 4-carboxybutyl chain at C-4 to give keto acid 5. The final cyclization to bicyclic compound 7b, a precursor to 1, was realized by a palladium-catalyzed intramolecular allylic amination of cis-allylic carbonate 6b that was elaborated from 5. 相似文献
42.
J Nagashima H Yamada S Ohkawa S Yonamine H Nishino A Yamagata Y Suzuki M Tanno K Chiba 《Radioisotopes》1986,35(12):631-635
The correlative study of myocardial perfusion assessed by 201Tl myocardial ECT with the pathological finding of the heart was performed in 10 autopsied cases with mean age of 77 years old (range: 60-90 y). In 6 cases with myocardial infarction (MI) 7 perfusion defects were observed, that was, 3 in anteroseptal wall, 1 in anterolateral wall and 3 in posterior wall on the images of SPECT. Seven MIs were also found in postmortem examination. Six MIs were observed at autopsy corresponding to perfusion defect on SPECT images. In one myocardial perfusion defect at inferoposterior portion on SPECT, a non-transmural MI was found at anteroseptum. In one case with valvular disease a false positive result was obtained at posterior wall where neither myocardial necrosis nor fibrosis was observed at autopsy. This case had aortic stenosis due to bicuspid aortic valve by autopsy. The ventricle was divided into 16 segments in each of 4 short axial images to evaluate extent of MI. SPECT for extent of MI showed sensitivity of 81.9%, specificity of 96.0% and diagnostic accuracy of 92.5%. False negative segment was apt to be observed at the surrounding of non-transmural MI or basal half of left ventricle (LV) with transmural MI, while false positive segment was at posterior portion of basal half of LV. It was concluded that myocardial ECT was useful for evaluation of the site and extent of MI. 相似文献
43.
Y. Yamada T. Kumagawa Y. T. Yamada T. Tominaga 《Journal of Radioanalytical and Nuclear Chemistry》1995,201(5):417-429
Mössbauer parameters of tin compounds, Sn(CH3)2H4–n (n=0, 1, 2, 3, 4), isolated in low temperature matrices were related to electronic properties at the tin nuclei obtained by molecular orbital calculations. Structures of novel species, Sn(CH3)2 and Sn(CH3)H, produced via photodissociation of matrix-isolated Sn(CH3)3H and Sn(CH3)2H2, respectively, were determined on the basis of molecular orbital calculations as compared with Mössbauer parameters. The correlations between Mössbauer quadrupole splitting and calculated electric field gradient using STO-3G or MINI-4 were found to depend on the valence of tin atoms because of poor allowance for basis sets in describing highly polar molecules. 相似文献
44.
H Aibata K Torizumi T Okada S Kiji R Yamada K Shimada K Taniguchi Y Aoki 《Radioisotopes》1987,36(11):594-596
In order to evaluate the gastric emptying and postprandial mixing of bile with food, the scintigraphies of hepatobiliary and gastrointestinal tracts by using three different kinds of radioisotopes were performed simultaneously (99mTc-E.HIDA for hepatobiliary scintigraphy, 111In-DTPA containing orange juice and 131I-albumin containing scrambled egg for gastrointestinal scintigraphy). This method was available for observation of gastric emptying of liquid and solid foods and also examination of the mixing effect of bile and food quantitatively. 相似文献
45.
Radical iodine atom transfer [3 + 2] cycloaddition with various alkenes using dimethyl 2-(iodomethyl)cyclopropane-1,1-dicarboxylate and 1,1-bis(phenylsulfonyl)-2-(iodomethyl)cyclopropane as new precursors of a homoallyl radical species smoothly proceeds to give functionalized cyclopentane derivatives in good yields. 相似文献
46.
Yoichi M.A Yamada 《Tetrahedron》2004,60(18):4087-4096
A novel catalyst PWAA, an assembled complex of phosphotungstic acid (H3PW12O40) and a non-cross-linked copolymer of N-isopropylacrylamide with an ammonium, was developed. It is an amphiphilic, cross-linked, and supramolecular insoluble complex and showed catalytic activity on oxidation with aqueous hydrogen peroxide. PWAA, used in 2.7×10−5-2.0×10−3 mol equiv., catalyzed oxidation of allylic alcohols, amines, and sulfides efficiently. The turnover number (TON) of PWAA reached up to 35,000. PWAA showed a good stability in organic/aqueous media and was reused three to five times. 相似文献
47.
Masatoshi Sakae Masanori Katsurada Mayumi Watanabe Fumio Yoneda Sadao Nishigaki Toshimasa Ishida 《Journal of heterocyclic chemistry》1997,34(1):157-160
The reaction of 2-bromoethylamine 1 with methylisothiocyanate 2 under mild condition gave 2-methyl-amino-2-thiazoline 3 as the major product together with two kinds of byproducts, 3-(N-methylthiocar-bamoyl)-2-methyliminothiazolidine 4 and N,N′-dimethyl-N-(2-thiazolin-2-yl)thiourea 5. Thermal isomer-ization of 5 to 4 was observed. The structures of the byproducts were confirmed by X-ray crystallography. 相似文献
48.
Attractive interactions between a thiocarbonyl group and a pyridinium nucleus, and between a carbonyl group and a pyridinium nucleus have been proven by (1)H and (13)C NMR studies, UV-vis spectral analyses, and X-ray crystallographic analyses of nicotinic amides 1 and 3, and pyridinium salts 2 and 4. Comparison of the Deltadelta values, which are the differences in the chemical shifts with reference compounds 5 or 6, showed that the absolute Deltadelta values of 2 and 4 are much larger than those of 1 and 3. In the UV-vis spectra, the n-->pi absorption of the C=S group of 2a exhibited a significant blue shift in CHCl(3). X-ray crystallographic analysis of 1-4 clearly showed that the C=S group of 2a and the C=O group of 4 are very close to the pyridinium moiety compared to the case of 1 and 3. In addition, the X-ray crystal packing structure of 2a showed the C=S group is sandwiched between two pyridinium rings. These experimental results strongly suggested the existence of attractive (C=S)...Py(+) and (C=O)...Py(+) interactions in solution and in crystal. The optimized geometries of 1 and 2 calculated at the HF/6-311G level are in good agreement with their X-ray geometries. MP2/6-311G calculations for the model systems of pyridinium salts 2 and 4 predicted that the electrostatic and induction energies are the major source of the attractive interactions. Since the larger contribution of electrostatic and induction interactions are characteristic features of cation-pi interactions, the (C=S)...Py(+) and (C=O)...Py(+) interactions would be classified as a cation-pi interaction. 相似文献
49.
Tabushi Iwao Kuroda Yasuhisa Yamada Masahiko Sera Takashi 《Journal of inclusion phenomena and macrocyclic chemistry》1988,6(6):599-603
Deuterium relaxation times ofd- andl--d-tryptophan included in -cyclodextrin derivatives were directly measured by deuterium NMR spectroscopy. The results showed that the molecular motion of the tryptophan molecule was strongly restricted even in the cavity of unmodified -cyclodextrin and the additional recognition groupings — ammonium and carboxylate — on -cyclodextrin did not affect the molecular motion of tryptophan, though the association constants were significantly enhanced.Deceased on March 22, 1987. 相似文献
50.
H Itokawa K Saitou H Morita K Takeya K Yamada 《Chemical & pharmaceutical bulletin》1992,40(11):2984-2989
Metabolites of antitumor cyclic hexapeptides, RA-VII and -X which were isolated from Rubia cordifolia were studied by hepatic microsomal biotransformation in rats and in bile juice of rabbits to which these drugs were administered intravascularly. Their structures and conformations were elucidated by two-dimensional nuclear magnetic resonance techniques, temperature effect on NH protons and nuclear Overhauser effect experiments. Specific N-demethylation of Tyr-3, O-demethylation and hydroxylation at aromatic rings of Tyr-3 and -5 were observed. Compared with metabolites of RA-VII, most of RA-X was excreted unchanged in the bile juice. Relationship among their structures, conformations and antitumor activities is also discussed. 相似文献