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531.
A novel class of 2-fluoro-6-O-propargyl-11,12-carbamate ketolide derivatives of erythromycin has been synthesized for antibacterial SAR studies. Replacement of the C2-hydrogen by a fluorine atom allows the synthesis of 6-O-propargylic ketones and electron-deficient 6-O-propargylic aromatic derivatives by preventing intramolecular C2-enolate Michael cyclization. 相似文献
532.
Phan NT Brown DH Adams H Spey SE Styring P 《Dalton transactions (Cambridge, England : 2003)》2004,(9):1348-1357
Solid-supported catalysts derived from homogeneous nickel(II) and palladium(II) non-symmetrical salen-type coordination complexes have been prepared and shown to be effective in the heterogeneous catalysis of carbon-carbon cross-coupling reactions. The nickel catalyst has been used in room-temperature Tamao-Kumada-Corriu reactions and the palladium catalyst in the Heck reaction at elevated temperatures. The complexes were prepared by improved methods and characterised by spectroscopic techniques. Comparisons between the solid-supported catalysts and their homogeneous analogues are reported. The single-crystal structure determination of the nickel and palladium complexes [M(salenac-OH)][M = Ni, Pd; salenac-OH = 9-(2',4'-dihydroxyphenyl)-5,8-diaza-4-methylnona-2,4,8-trienato](2-)] is reported. 相似文献
533.
Tuan D. Phan 《Tetrahedron letters》2005,46(3):397-400
Remarkable efficiency of hydrogen peroxide utilization is reported for oxygenation of four organic sulfides catalyzed by a divacant lacunary silicotungstate, (Bu4N)4[γ-SiW10O34(H2O)2] (1), under mild conditions. The addition of imidazole, phosphate, or carboxylates significantly enhances the rate of organic sulfide oxygenation. Most notably, use of 1 and imidazole, both at 1% molar concentration, resulted in the quantitative conversion of phenylsulfide to sulfoxide with 1 equiv of H2O2 in 3 h, and to sulfone with 2 equiv of H2O2 in 6 h. 相似文献
534.
Hanessian S Papeo G Fettis K Therrien E Viet MT 《The Journal of organic chemistry》2004,69(15):4891-4899
A bicyclic indolizidinone carboxylic acid and a tricyclic constrained analogue of l-proline were synthesized and evaluated for their ability to induce helix formation as l-Ala tetrapeptides. Variable-temperature NMR, DMSO titration, CD spectra, and X-ray structure analyses, in conjunction with molecular modeling, confirmed the existence of 3(10)-helical motifs with di- and tetrapeptides of l-Ala. 相似文献
535.
The tris(tetra-n-butylammonium) salt of thiopyrophosphate 5 was prepared from trimethyl phosphate in four steps. Treatment of geranyl bromide with 5 gave an 80% yield of geranyl S-thiolodiphosphate (6). Thiolodiphosphate 6 is substantially less reactive than geranyl diphosphate (7) in the prenyl transfer reaction catalyzed by farnesyl diphosphate synthase and is a good inhibitor of the enzyme. 相似文献
536.
Thiolo thiophosphate analogues of isopentenyl diphosphate (IPP), dimethylallyl diphosphate (DMAPP), geranyl diphosphate (GPP), farnesyl diphosphate (FPP), and geranylgeranyl diphosphate (GGPP) were synthesized. Inorganic thiopyrophosphate (SPP(i)) was prepared from trimethyl phosphate in four steps. The tris(tetra-n-butylammonium) salt was then used to convert isopentenyl tosylate to (S)-isopentenyl thiodiphosphate (ISPP). (S)-Dimethylallyl (DMASPP), (S)-geranyl (GSPP), (S)-farnesyl (FSPP), and (S)-geranylgeranyl thiodiphosphate (GGSPP) were prepared from the corresponding bromides in a similar manner. ISPP and GSPP were substrates for avian farnesyl diphosphate synthase (FPPase). Incubation of the enzyme with ISPP and GPP gave FSPP, whereas incubation with IPP and GSPP gave FPP. GSPP was a substantially less reactive than GPP in the chain elongation reaction and was an excellent competitive inhibitor, K(I)(GSPP) = 24.8 microM, of the enzyme. Thus, when ISPP and DMAPP were incubated with FPPase, GSPP accumulated and was only slowly converted to FSPP. 相似文献
537.
Trong Nghia Ngo Nu Dan Phuong Nguyen Ngoc Thien Ly Nguyen Nguyen Kim Tuyen Pham Nhat Minh Phan Trong Dat Bui 《Natural product research》2020,34(13):1820-1826
AbstractFrom the leaves of Markhamia stipulata var. canaense V.S. Dang, one new phytosphingolipid, named markhasphingolipid A (6) together with five known compounds, 4’,7-O-dimethylapigenin (1), narigenin (2), tectoquinone (3), mollic acid (4), 1-hexadecanoyl-sn-glycerol (5) were classified by various chromatographic methods. Their structures were designated by IR, UV, HR-ESI-MS, HR-ESI-MS/MS and NMR experiments. All compounds were recognized for the first time from this species. The cytotoxicity of all n-hexane fractions and isolated compounds (5 & 6) against three human cancer cell lines (HeLa, HepG2, and MCF-7) were evaluated by SRB assay. All n-hexane fractions expressed cytotoxic effect on three tested cancer cell lines (at the concentration of 100?μg/mL, percent of cytotoxicity ranged from 55.81% to 95.83%) as well as compound 5 (IC50 ranged from 48.51 to 63.30?μM) whereas fraction H.I and compound 6 did not show activity. 相似文献
538.
The far infrared spectrum [350 to 25 cm–1] of gaseous chloroacetaldehyde, ClCH2CHO, has been recorded at a resolution of 0.10 cm–1. The first excited-state transition of the asymmetric torsion of the more stable near s-cis [chlorine atom s-cis to the aldehyde hydrogen atom] conformer has been observed at 26.9 cm–1, with seven additional upper state transitions falling to higher frequency. Additionally, the fundamental torsional transition of the s-trans conformer has been observed at 58.9 cm–1 with two excited states also falling to higher frequency. From these data, the asymmetric torsional potential coefficients have been determined to be:V
1=414±11;V
2 = 191±3;V
3=–203±5;V
4=44±1 andV
6=–26±1 cm–1. The s-cis to s-trans barrier is 500±5 cm–1 (1.43±0.01 kcal mol–1) with the s-cis conformer being more stable by 267±19 cm–1 (0.76±0.05 kcal mol–1) than the s-trans form. The Raman [4000 to 100 cm–1] and infrared (4000 to 400 cm–1] spectra of the gas have been recorded. Additionally, the Raman spectrum of the liquid has been recorded and qualitative depolarization values obtained. Complete vibrational assignments are proposed for both conformers based on band contours, depolarization values, and group frequencies. The assignments are supported by ab initio Hartree-Fock gradient calculations employing the 3–21G* basis set to obtain the frequencies and the potential energy distributions for the normal vibrations for both rotamers. Additional ab initio calculations at the MP4/6-31G* level have been carried out to determine the structural parameters for both conformers. The results are discussed and compared with the corresponding quantities obtained for some similar molecules.This contribution taken in part from the thesis of C. L. Tolley which will be submitted to the Department of Chemistry in partial fulfillment of the Ph.D. degree. 相似文献
539.
Phan V?n Chuong 《Journal of Mathematical Analysis and Applications》1981,82(2):473-490
The following results are proved: (1) X be either a locally convex Lusin space1 or a locally convex metrizable (not necessarily separable) space, let Γ be a weakly upper semicontinuous random multimapping defined on a convex compact subspace of X taking convex weakly compact values and satisfying the Browder-Halpern's “inward” condition. Then Γ has a fixed point. (2) In an arbitrary metric space, a continuous random multimapping Γ (with stochastic complete domain) has fixed points, whenever the corresponding deterministic fixed point theorem for Γ holds. 相似文献
540.
Nam T.S. Phan 《Tetrahedron》2005,61(51):12065-12073
A polymer-supported palladium(II) salen-type complex exhibited catalytic activity in the cross-coupling reaction of various aryl bromides and heteroaryl bromides with phenylboronic acid in a mini-continuous flow reactor system at elevated temperatures in a phosphine-free system. The reaction was also performed in batch using a number of different solvent systems in order to optimise conditions. The catalytic mini-reactor can be used repeatedly over several cycles in the Suzuki-Miyaura cross-coupling reaction. While the diameter of the flow channel is 3 mm, the macroporous resin supported catalyst is solvent expanded to completely fill the channel. Consequently, the liquid path is through the micro channels of the macroporous resin structure. Intensification of the process over the stirred batch reaction is through increased reagent-catalyst contact and results in a 20-fold increase in the rate of reaction. The residence/space time on the reactor is 10.5 min, compared to 24 h in batch, which means that a diversity of starting materials can be screened over a short period of time. To demonstrate the utility of the system, a diversity of aryl and heteroaryl bromides have been studied. 相似文献