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41.
Takami H Nonaka H Kishibayashi N Ishii A Kase H Kumazawa T 《Chemical & pharmaceutical bulletin》2000,48(4):552-555
A series of 4-phenoxybutyric acid derivatives attached to a tricyclic skeleton were prepared and evaluated as 5alpha-reductase inhibitors. Structure activity relationships for these compounds in terms of rat epididymis (type 2) 5alpha-reductase inhibitory activities reveal that 1) the substitution pattern at the 11-position of dibenz[b,e]oxepin influenced potency, 2) higher lipophilicity of the tricyclic skeleton improved potency, whereas the existence of a basic nitrogen atom in this skeleton was detrimental to potency, and 3) isobutyl substitution at the 8 positon of the azepine skeleton was tolerated. Among the tricyclic compounds studied, 4-[3-[5-benzyl-8-(2-methyl)propyl-10,11-dihydrodibenz[b,f]azepine- 2-carboxamido]phenoxy]butyric acid (26) was the most potent inhibitor of rat type 2 5alpha-reductase at 0.1 microM. 相似文献
42.
Treatment of the hydrosulfido-bridged titanium-ruthenium heterobimetallic complex [Cp2Ti(mu2-SH)2RuCl(eta5-C5Me5)] (1; Cp = eta5-C5H5) with an excess of triethylamine followed by addition of [RuCl2(PPh3)3] and [[(cod)M]2(mu2-Cl)2] (M = Rh, Ir; cod = 1,5-cyclooctadiene) led to the formation of the TiRu2 and TiRuM mixed-metal sulfido clusters [(CpTi)[(eta5-C5Me5)Ru][Ru(PPh3)2](mu3-S)2(mu2-Cl)2] (3) and [(CpTi)[(eta5-C5Me5)Ru][M(cod)](mu3-S)2(mu2-Cl)] (M = Rh (4a), Ir (4b)), respectively. On the other hand, the reactions of 1 with [M(PPh3)4] (M = Pd, Pt) afforded the TiRuM trinuclear clusters [(CpTiCl)[(eta5-C5Me5)Ru][M(PPh3)2](mu3-S)(mu2-S)(mu2-H)] (M = Pd (5a), Pt (5b)) with an unprecedented M3(mu3-S)(mu2-S) core. The detailed structures of these triangular clusters 3-5 have been determined by X-ray crystallography. Crystal data: 3, triclinic, P1, a = 12.448(4) A, b = 12.773(4) A, c = 17.270(4) A, alpha = 100.16(2) degrees, beta = 99.93(2) degrees, gamma = 114.11(3) degrees, V = 2373(1) A(3), Z = 2; 4a, triclinic, P1, a = 7.714(2) A, b = 11.598(3) A, c = 14.802(4) A, alpha = 80.46(2) degrees, beta = 82.53(2) degrees, gamma = 71.47(2) degrees, V = 1234.0(6) A3, Z = 2; 4b, triclinic, P1, a = 7.729(1) A, b = 11.577(2) A, c = 14.766(3) A, alpha = 80.14(1) degrees, beta = 82.71(1) degrees, gamma = 71.55(1) degrees, V = 1231.1(4) A3, Z = 2; 5a, monoclinic, P2(1)/c, a = 11.259(4) A, b = 16.438(4) A, c = 26.092(5) A, beta = 102.23(3) degrees, V = 4719(2) A(3), Z = 4; 5b, monoclinic, P2(1)/n, a = 11.369(2) A, b = 16.207(3) A, c = 26.116(2) A, beta = 102.29(1) degrees, V = 4701(1) A3, Z = 4. 相似文献
43.
The lankacidin biosynthetic gene cluster in Streptomyces rochei strain 7434AN4 was found to span 31 kb of the giant linear plasmid pSLA2-L and contain a polyketide synthase (PKS)/nonribosomal peptide synthetase (NRPS) hybrid gene (lkcA), type I PKS genes, and pyrroloquinoline quinone (PQQ) biosynthetic genes (lkcK-lkcO). Feeding of PQQ to a pqq mutant restored the lankacidin production, suggesting its crucial role in an oxidation process. However, formation of the 17-membered macrocyclic ring was not catalyzed by PQQ-dependent dehydrogenase (Orf23), but was by flavin-dependent amine oxidase (LkcE). Compound LC-KA05 isolated from an lkcE disruptant was an acyclic intermediate lacking the C2-C18 linkage. These results suggested a cyclization mechanism for the synthesis of the lankacidin macrocyclic skeleton. 相似文献
44.
Wickramasinghe NP Shaibat M Ishii Y 《Journal of the American Chemical Society》2005,127(16):5796-5797
High-resolution NMR spectroscopy for paramagnetic complexes in solids has been rarely performed because of its limited sensitivity and resolution due to large paramagnetic shifts and associated technical difficulties. The present study demonstrates that magic angle spinning (MAS) at speeds exceeding 20 kHz provides unusually high sensitivity and excellent resolution in 1H solid-state NMR (SSNMR) for paramagnetic systems. Spinning-speed dependence of 1H MAS spectra showed that very fast MAS (VFMAS) at 24-28 kHz enhanced sensitivity by a factor of 12-18, compared with the sensitivity of 1H SSNMR spectra under moderate MAS at 10 kHz, for Cu(dl-alanine)2.H2O and Mn(acac)3, for which the spectral ranges due to 1H paramagnetic shifts reach 200 and 1000 ppm, respectively. It was theoretically and experimentally confirmed that the absolute sensitivity of 1H VFMAS for small paramagnetic complexes such as Cu(dl-alanine)2 can be an order of magnitude higher than that of equimolar diamagnetic ligands because of short 1H T1 ( approximately 1 ms) of the paramagnetic systems and improved sensitivity under VFMAS. On the basis of this demonstrated high sensitivity, 1H SSNMR micro analysis of paramagnetic systems in a nanomole scale is proposed. Applications were performed on two polymorphs of Cu(II)(8-quinolinol)2, which is a suppressor of human cancer cells. It was demonstrated that 1H VFMAS SSNMR spectra accumulated for 20 nmol of the polycrystalline samples in 10 min enabled one to distinguish alpha- and beta-forms of Cu(II)(8-quinolinol)2 on the basis of shift positions and line widths. 相似文献
45.
Y. Kuwahara H. Fukami R. Howard S. Ishii F. Matsumura W.E. Burkholder 《Tetrahedron》1978,34(12):1769-1774
Chemical an spectroscopic evidence is presented to show that 2,3-dihydro-2,3,5-trimethyl-6-(1-methyl-2-oxobutyl)-4H-pyran-4-one (10) is the sex pheromone produced by the female drugstore beetle, Stegobium paniceum L. 相似文献
46.
A series of iminodiacetic acid (IDA)-linked polyamides (DpPyPyPy-IDA-PyPyPyDp) were prepared and constitute polyamides joined head-to-head by a functionalizable five-atom linker. It was found that the IDA linker exerts a unique influence over the DNA binding conformation differing from both the beta-alanine (extended) or gamma-aminobutyric acid (hairpin) linkers, resulting in cooperative parallel side-by-side 2:1 binding in an extended conformation most likely with a staggered versus stacked alignment. A generalized variant of a fluorescent intercalator displacement (FID) assay conducted on a series of hairpin deoxyoligonucleotides containing a systematically varied A/T-rich binding-site size was used to distinguish between the binding modes of the IDA-linked polyamides. 相似文献
47.
Photochemistry of ε,ζ-Methano-α,γ-dienones and 7,8-Methano-1,3,5-trienes Irradiation of the δ-cyclopropyl-dienone (E)- 6 (λ ≥ 347 nm) gives (Z)- 6, 10 (1,5-sigmatropic H-shift), (E/Z)- 9 (electrocyclic process involving C(ε), C(ζ)-cleavage) and 11 (ring opening). The corresponding 6-cyclopropyl-triene (E)- 7 gives on singlet excitation (δ > 280 nm) 14 (1,5-sigmatropic H-shift) and, to a smaller extent, the bicyclo [3.2.0] heptenyl-dienes (E/Z)- 13 . However, on triplet excitation (λ ≥ 347 nm, benzophenone) (E)- 7 gives (E/Z)- 13 as the main products. On both 1π,π*- and 3π,π*-excitation, (Z)- 7 and 15 are formed in small amounts. 相似文献
48.
Clot O Akahori Y Moorlag C Leznoff DB Wolf MO Batchelor RJ Patrick BO Ishii M 《Inorganic chemistry》2003,42(8):2704-2713
The preparations of two new phosphinothiophene ligands, 3,3'-bis(diphenylphosphino)-2,2'-bithiophene (dppbt; 1) and 3,3' "-dihexyl-3',3' '-bis(diphenylphosphino)-2,5':2',2' ':5' ',2' "-quaterthiophene (hdppqt; 2) are reported. Oxidation of 1 gives 3,3'-bis(diphenylphosphine oxide)-2,2'-bithiophene (3), and the crystal structure of this compound was determined. Pd(II) and Au(I) complexes of these ligands have been synthesized and characterized. Crystal structures of [(dppbt)PdCl(2)] (1-Pd), [(hdppqt)PdCl(2)] (2-Pd), [(dppbt)(AuCl)(2)] (1-Au), and [(hdppqt)(AuCl)(2)] (2-Au) were obtained. [(dppbt)(AuCl)(2)] crystallized in two solid-state forms; crystals grown from CH(2)Cl(2)/Et(2)O show a gold-gold interaction of 3.3221(4) A, but from CH(2)Cl(2)/toluene, the molecule crystallizes as a toluene adduct (1-Au-tol) and does not show any gold-gold interaction. All the complexes were characterized via UV-vis spectroscopy and cyclic voltammetry, and the effect of the metal on the energy of the pi-pi transition and oxidation potential was determined. These data are correlated to the interannular torsion angles in the oligothienyl groups from the crystal structure studies. 相似文献
49.
50.