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81.
Stuart Lang Neil Muir Franziska Schönebeck Andrew H. Payne 《Tetrahedron letters》2005,46(23):4027-4030
The phosphorus based radical precursors N-ethylpiperidine hypophosphite (EPHP) and diethylphosphine oxide (DEPO) are efficient reagents for carrying out the formation of seven- and eight-membered rings. Esters and amides were successfully converted into the corresponding eight-membered lactones and seven- and eight-membered lactams in good to excellent yields. 相似文献
82.
Two iminosugars have been designed and synthesized as potential inhibitors of UDP-Galf transferase, an enzyme involved in Mycobacterium tuberculosis cell wall biosynthesis. The design is based on a proposed model of the transition state for the transferase reaction. One of the two racemic compounds is the first reported inhibitor of the target enzyme from M. smegmatis. 相似文献
83.
Two reactions, catalyzed by lactate oxidase (LO) and peroxidase, are initiated by a single injection of the enzymes and the substrate 2,2'-azino-bis(3-ethylene-thiazoline-6-sulfonic acid) (ABTS) into the capillary previously filled with the sample (lactate or lactate-oxalate mixture) and the run buffer containing NADH. The oxidized ABTS product upon reaction with NADH is converted to NAD(+) which is separated and detected in less than 2 min at 266 nm with a sample throughput of 7 min (including wash steps between samples). Simplex trade mark software is used to optimize the enzyme concentrations and reaction temperature. Consumption of the more expensive LO enzyme is only 1.4 x 10(-3) U per assay assuming 27 nL per injection. Linearity is established within the range from 0.0025 to 1 mM with R(2) of 0.9982. Recoveries of lactate from five spiked serum samples averaged 101%. Application of this method for the determination of oxalate as an inhibitor of LO is demonstrated. 相似文献
84.
[reaction: see text] The title alkaloid was synthesized in racemic form from 3,7-diallyl-2,4,6,8-tetraoxo-3,7-diazabicyclo[3.3.1]nonane (7) by a regioselective diallylation reaction followed by double ring-closing olefin metathesis and exhaustive reduction. Tetraoxobispidine 7 was itself prepared in three simple operations from dimethyl malonate. The entire sequence to alpha-isosparteine was conducted on a multigram scale and proceeded without recourse to chromatography. 相似文献
85.
Recovery of intact proteins from silver stained gels 总被引:1,自引:0,他引:1
Silver stained proteins of a wide molecular weight (MW) range (20-116 kDa) were successfully recovered by both electroblot and electroelution. The recovery was demonstrated for nanogram loads of proteins separated by SDS-PAGE and visualized by silver staining methods compatible and incompatible with mass spectrometry (MS). It was shown that the alcohol/acid and glutaraldehyde fixation steps present in a number of staining procedures did not prevent recovery of intact proteins from gels. It was found that the recovery of intact proteins from silver stained gels was substantially increased upon pre-equilibration in a buffer containing the reducing agent, dithiothreitol (DTT). The effect of destaining on the recovery of silver stained proteins was also investigated. Comparable recovery of intact proteins within a wide MW range from silver stained gels with and without destaining step was demonstrated. Recovery of model proteins from gels visualized using silver staining method compatible with MS showed 52 to 76% yield of that from the unstained gel, depending upon method of the transfer. Comparison of the recovery of intact proteins from gels visualized using other staining procedures was also made. The above findings have implications as to the supposed irreversible nature of protein "fixation" inside polyacrylamide matrix, and confirm lack of binding of proteins in the gel to metal silver deposited on its surface. This method has the potential to be suitable for direct characterization of proteins by matrix-assisted laser desorption ionization-mass spectrometry (MALDI-MS) without additional purification steps. 相似文献
86.
1-Phenyl-2-(benzenesulphonyl)-ethylene and 1-phenyl-2-(benzenesulphonyl)-prop-1-ene have been shown to undergo ,-photoisomerisation, whereas 2-benzenesulphonylindene readily forms [π2 + π2] photoadducts with 2,3-dimethylbut-2-ene, cyclopentene, and cyclohexene. 相似文献
87.
Summary Benzothiazole-2-selenone, BTSeH, was prepared by treating 2-chlorobenzothiazole with Na2Se, and the 6-ethoxy analogue (EtOBTSeH) was obtained similarly. From BTSeH, the species [R4N][BTSe] (R=Me, Et Bu-n), Zn-(BTSe)2(pyr)2, (BTSe–)2, Zn(BTSe-)2I2 and Me2C=CH-CH(SSeTB)Me were obtained. Addition of [n-Bu4N] [BTSe] to [Zn(BTSe)2]
n
afforded [n-Bu4N] [Zn(BTSe)3(H2O)]. The Se n.m.r. spectra of these species are briefly reported. 相似文献
88.
Badham NF Mendelson WL Allen A Diederich AM Eggleston DS Filan JJ Freyer AJ Killmer LB Kowalski CJ Liu L Novack VJ Vogt FG Webb KS Yang J 《The Journal of organic chemistry》2002,67(15):5440-5443
A convenient two-step homologation of both aliphatic and aromatic ketones to the corresponding carboxylic acid has been developed. First ketones were converted to epoxynitriles with the Darzens reaction. Second, a Lewis acid mediated rearrangement of these epoxynitriles with lithium bromide was achieved to give homologated secondary alkanoic acids (as well as aryl-alkanoic) in good yields. The mechanism and the scope of the rearrangement reaction were investigated. This strategy constitutes a two-step homologation of ketones to secondary carboxylic acids. 相似文献
89.
The 2,2-diphenylcyclopropyl group was employed to accelerate reactions of alpha-methoxy radicals containing beta-leaving groups, to trap the products of either migration or heterolysis of the leaving group, and to provide a useful chromophore for laser flash photolysis kinetic studies. The reporting group biases reactions in favor of heterolytic fragmentation and most likely intercepts radical cations in ion pairs. The 1-methoxy-1-methyl-2-(diethylphosphatoxy)-2-(2,2-diphenylcyclopropyl)ethyl radical (3a) reacted faster than the kinetic resolution of the instrument (k > 2 x 10(8) s(-1)) in all solvents studied, and the 2-acetoxy analogue (3b) reacted much faster than related radicals that do not contain the cyclopropyl group (e.g., k = 1.1 x 10(6) s(-1) in CH3CN at ambient temperature). The rate constants and Arrhenius parameters for reactions of 3b indicated that the rate-limiting step in the reaction was heterolytic cleavage. The 1,2-dimethoxy-1-methyl-2-(2,2-diphenylcyclopropyl)ethyl radical (26) reacted in a general acid-catalyzed heterolysis reaction, and rate constants for protonation of the beta-methoxy group by a series of carboxylic acids were determined. The results suggest that acid-catalyzed reactions of beta-alkoxy radicals might be employed in synthetic conversions. 相似文献
90.
Neil Bartlett Sam Yeh Kostantinos Kourtakis Tom Mallouk 《Journal of fluorine chemistry》1984,26(1):97-116
Iridium hexafluoride oxidizes ReF6 (via an ReF6+ salt) and at room temperatures IrF6, ReF6, ReF7 and (IrF5)4 are each present in the equilibrium mixture. From these and related findings: ΔH°(ReF6 → ReF6+ + e?) 1092 ± 27 kj mole?1(261 ± 6 kcal mole?1), and thermodynamic data are selected to yield ΔH°(ReF7(g) → ReF6+(g) + F?(g))=893 ± 33 kj mole?1(213 ± 8 kcal mole?1). From observations on the stability of IF6+BF4? and the lattice enthalpy evaluation for the salt, ΔH°(IF7(g) → IF6+(g) + F?(g))= 870 ± 24 kj mole?1(208 ± 6 kcal mole?1). 相似文献