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141.
142.
Valahovic MT Gunnoe TB Sabat M Harman WD 《Journal of the American Chemical Society》2002,124(13):3309-3315
A series of complexes of the form TpRe(CO)(L)(eta(2)-naphthalene) (Tp = hydridotris(pyrazolyl)borate) undergoes tandem electrophile/nucleophile addition reactions with a high degree of regiocontrol depending on the auxiliary ligand, L. When L = PMe(3), the reaction of the eta(2)-naphthalene complex with triflic acid followed by a silyl ketene acetal favors the 1,4-addition product, whereas when L = pyridine, N,N-dimethylaminopyridine, N-methylimidazole, or NH(3) the 1,2-addition product is favored. These reactions proceed with excellent stereocontrol: both electrophile (H(+), D(+)) and nucleophile (silyl ketene acetal) add anti to the face of metal coordination, and a single coordination diastereomer can be isolated for each reaction. One-electron oxidation of the Re complex affords the corresponding free dihydronaphthalene in good yield. 相似文献
143.
Y Akiyama N Yui T Matsumoto T Iinuma T Ishikawa T Nakajima K Machida J Nishikawa M Iio K Uno 《Radioisotopes》1988,37(3):140-147
The value of preoperative bone scans in patients with primary breast and prostate cancer was evaluated prospectively. Of 414 patients with breast cancer, clinical stage I is 14, II is 219, IIIA is 59, IIIB is 39 and IV is 14. Of 88 patients with prostate cancer, clinical stage I is 14, II is 15, III is 18 and IV is 41. 11 percent of patients with breast cancer and 54 percent of patients with prostate cancer had bone metastases. Clavicle, ribs, thoracic spine, lumbar spine and pelvis metastasized most frequently. The incidences of bone metastases were 18.4% with Scirrhous carcinoma, 15.4% with Medullary tubular carcinoma and 3.8% with Papillotubular carcinoma. The methodology and results of ROC analysis were described in our other papers. Some results of data analysis were described in this paper. 相似文献
144.
Michael I. Bruce Andrew Catlow Mark G. Humphrey George A. Koutsantonis Michael R. Snow Edward R.T. Tiekink 《Journal of organometallic chemistry》1980,338(1):59-80
A reinvestigation of the reaction between C2(CO2Me)2 and RuH(PPh3)2(η-C5H5) and some related complexes is reported. Initial cis addition is followed by conversion into the trans isomer. In the case of the bis-(PPh3) complex, isomerisation is followed by chelation of the ester CO group with concomitant displacement of one PPh3ligand. The resulting chelate complex reacts with CO or CNBut to give the (Z)-RuC(CO2Me)CH(CO2Me) complexes; the (E)-isomer of the carbonyl complex is obtained by addition of C2(CO2Me)2to RuH(CO)(PPh3)(η-C5H5). The 1Hand 13C NMR spectra are not a reliable guide to assignment of the stereochemistry of the vinyl group. Other products isolated from the initial reaction are the bis-insertion product CH(CO2Me)} -(PPh3)(η-C5H5) and the 1/2 PPh3/C2(CO2Me)2 adduct. The molecular structures of Ru{(Z)-C(CO2Me)CH(CO2Me)}(CO)(PPh3(η-C5H5) · 0.5EtOH, Ru{(E)-C(C2Me)CH(CO2Me)}(dppe)(η-C5H5) and CH(CO2Me)}(PPh3)(η-C5H5) have been determined. The cis isomer is monoclinic, space group P21,with a 9.328(8), b 17.385(10), c 10.356(7) Å, β 101.78(3)° and Z = 2; 2107 data with I ≥ 2.5σ(I) were refined to R = 0.076 Rw = 0.085. The trans isomer is triclinic, space group P, with a 10.404(7) b 11.221(6), c 13.230(9) Å, α 92.67(5), β 110.56(5), γ 106.21(5)° and Z = 2; 2520 data with I ≥ 2.5σ(I) were refined to R = 0.055 Rw = 0.068. The butadienyl complex is monoclinic, space group P21/a, with a 19.655(8), b 8.674(4), c 21.060(5) Å, β 116.22(3)° and Z = 4; 2724 data with I ≥ 2.5σ(I) were refined to R = 0.042, Rw = 0.047. 相似文献
145.
John T. Shaw Christine E. Brotherton Robert W. Moon Mark D. Winland Mark D. Anderson Keith S. Kyler 《Journal of heterocyclic chemistry》1980,17(1):11-16
A much improved synthesis of the heretofore difficultly obtainable 2,6-diaminopyrazine (4) was afforded by the low-pressure catalytic hydrogenation (palladium on carbon) of 2,6-diazido-pyrazine (2) ; reaction of 2,6-dichloropyrazine (1) and sodium azide gave 2 in 84% yield. The outcome of the reduction was found to be solvent dependent: 1,2-dimethoxyethane containing aqueous ammonia gave 4 in 83% yield; 1,2-dimethoxyethane alone gave 5-aminotetrazolo[1,5-a]-pyrazine (3) in 26% yield. Additional alternative syntheses of 3 and 4 are described. A number of acyl and azo derivatives of 4 were prepared. Reactions of 2 with dimethyl acetylenedicarboxylate and ethyl acetate (base catalyzed) leading to vic-triazole derivatives are also described. 相似文献
146.
Krishna Gopal Dongol M. Cristina Melo e Silva Kouki Matsubara Taisuke Matsumoto Shuntaro Mataka Thies Thiemann 《无机化学与普通化学杂志》2003,629(6):945-947
The preparation of two η6‐estra‐1, 3, 5(10), 6‐tetraene tricarbonylchromium complexes 4 and 6 are described. In both cases only one stereoisomer can be isolated, in contrast to other estrane‐tricarbonylchromium complexes, where complexations are non‐stereoselective. X‐ray crystal structural analysis of 4 discloses that only the more sterically hindered β‐facial isomer is formed. It is assumed that the 6, 7‐olefinic moiety exerts a directive influence on the complexation. 相似文献
147.
Mark Salomon 《Journal of solution chemistry》1990,19(12):1225-1236
Conductivity data are used to determine thermodynamic complex formation constants for cases in which both the initial electrolyte and the complexed electrolyte form ion pairs. Using the method described in the text, the complex formation constants of Li+, Na+ and K+ with the crown ether 18-crown-6 and of Li+ with the ligand triphenylphosphine oxide in propylene carbonate have been evaluated from conductance data. The complexation of AgBr in propylene carbonate solutions of n-etrabutylammonium bromide has also been studied by the measurement of molar conductivities. The results of these studies indicate that ion pairing should not be neglected, even in high permittivity solvents such as propylene carbonate, and that the ion pair association constants correlate well with structural studies on cation-crown ether molecular conformations. 相似文献
148.
The asymmetric total synthesis of (-)-reveromycin A is described. The key steps involved a Lewis acid catalyzed inverse electron demand hetero-Diels-Alder reaction followed by hydroboration/oxidation to afford the spiroketal core 4 in a highly stereoselective manner and introduction of the C18 hemisuccinate by high-pressure acylation. 相似文献
149.
Kakiuchi F Tsuchiya K Matsumoto M Mizushima E Chatani N 《Journal of the American Chemical Society》2004,126(40):12792-12793
Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes involving triethyl-, dimethylphenyl-, tert-butyldimethyl-, and triphenylsilanes can be used as a silylating reagent. Coordination of an sp2 nitrogen atom to the ruthenium complex is important for achieving this silylation reaction. 相似文献
150.