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排序方式: 共有101条查询结果,搜索用时 351 毫秒
1.
J Deutsch L Hegedus N H Greig S I Rapoport T T Soncrant 《Journal of chromatography. A》1992,579(1):93-98
Nicotine and its metabolite, cotinine, were measured in rat plasma and brain by gas chromatography-mass spectrometry. Both agents were extracted from plasma and brain, separated on a capillary column, and quantified by single-ion monitoring. The major fragment ions of nicotine and cotinine at m/z 84 and m/z 98, respectively, were monitored by electron-impact ionization detection and the protonated molecular ions at m/z 163 and m/z 177, respectively, were monitored by chemical ionization detection. Both compounds were quantified using deuterium-labeled nicotine and cotinine, respectively, as internal standards. 相似文献
2.
Hegedus LS Geisler L Riches AG Salman SS Umbricht G 《The Journal of organic chemistry》2002,67(22):7649-7655
Butenolides 5a and 13 were used as optically active templates in the de novo synthesis of 4'-disubstituted nucleoside analogues. The butenolides were reduced and acylated in situ to give acetates 10 and 14. Vorbrüggen coupling gave the protected nucleoside analogues 11 and 15. Reduction of 11 gave 4'-ethoxy-2',3'-dideoxythymidine (6) and deprotection of 15 gave 4'-ethoxy-2',3'-dideoxydidehydrothymidine (7). The cis-dihydroxylation of a variety of butenolides occurred with the major product formed from oxidation of the beta-face. 相似文献
3.
The photochemical reaction between optically active ene carbamates and chromium alkoxycarbene complexes containing unsaturated aliphatic side chains was further developed. Although remote olefinic groups, including conjugated dienes, were tolerated, a homoallylic side chain underwent intramolecular reaction to give a strained cyclobutanone. (+)-Cerulenin was synthesized utilizing the photochemical reaction of an alkynylcarbene complex with an optically active ene carbamate and the bis(pi-crotyl)nickel halide alkylation of a vinyl bromide as key steps. 相似文献
4.
Louis S. Hegedus 《Angewandte Chemie (International ed. in English)》1988,27(9):1113-1126
The use of transition-metal complexes as reagents for the synthesis of complex organic compounds has been under development for at least several decades, and many extraordinary organic transformations of profound potential have been realized. However, adoption of this chemistry by the practicing synthetic organic chemist has been inordinately slow, and only now are transition-metal reagents beginning to achieve their rightful place in the arsenal of organic synthesis. Several factors contributed to the initial reluctance of synthetic organic chemists to use organometallic reagents. Lacking education and experience in the ways of elements having d electrons, synthetic chemists viewed organometallic processes as something mysterious and unpredictable, and not to be discussed in polite society. Organometallic chemists did not help matters by advertising their latest advances as useful synthetic methodology, but restricting their studies to very simple organic systems lacking any serious functionality (e.g., the “methyl, ethyl, butyl, futile” syndrome). Happily, things have changed. Organometallic chemists have turned their attention to more complex systems, and more recently trained organic chemists have benefited from exposure to the application of transition metals. This combination has set the stage for major advances in the use of transition metals in the synthesis of complex organic compounds. This review deals with one aspect of this area, the use of transition metals in the synthesis of indoles. 相似文献
5.
Kristina Hetherington Dr. Zsofia Hegedus Dr. Thomas A. Edwards Dr. Richard B. Sessions Prof. Adam Nelson Prof. Andrew J. Wilson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(34):7638-7646
Protein–protein interactions (PPIs) control virtually all cellular processes and have thus emerged as potential targets for development of molecular therapeutics. Peptide-based inhibitors of PPIs are attractive given that they offer recognition potency and selectivity features that are ideal for function, yet, they do not predominantly populate the bioactive conformation, frequently suffer from poor cellular uptake and are easily degraded, for example, by proteases. The constraint of peptides in a bioactive conformation has emerged as a promising strategy to mitigate against these liabilities. In this work, using peptides derived from hypoxia-inducible factor 1 (HIF-1α) together with dibromomaleimide stapling, we identify constrained peptide inhibitors of the HIF-1α/p300 interaction that are more potent than their unconstrained sequences. Contrary to expectation, the increased potency does not correlate with an increased population of an α-helical conformation in the unbound state as demonstrated by experimental circular dichroism analysis. Rather, the ability of the peptide to adopt a bioactive α-helical conformation in the p300 bound state is better supported in the constrained variant as demonstrated by molecular dynamics simulations and circular dichroism difference spectra. 相似文献
6.
4'-Substituted nucleoside analogues have been synthesized using palladium-catalyzed asymmetric allylic amination conditions. A kinetic discrimination between the diastereomeric lactol acetates (3) produced the desired aminated products (6a-d) and recovered acetate (alpha-3) in high yields and <97:3 diastereoselectivity. Epimerization of the recovered lactol acetate (alpha-3) produced a 60:40 alpha/beta mixture of (3), which could be resubjected, in principle, to the palladium-catalyzed asymmetric allylic amination conditions. 相似文献
7.
8.
Both tri- and tetra(ethylene glycol) linked bis-chromium carbene complexes have been synthesized. These carbene complexes were photolyzed with N-protected imidazolines to give protected azapenams. These were transformed into polyether-linked basket dioxocyclams 4a,b and bis-dioxocyclams 5a,b. These compounds have cavities for the complexation of both "hard" and "soft" metal ions. The complexes of Ni, Ba, and Gd were synthesized. 相似文献
9.
Hegedus L Kirschner N Wittmann M Simon P Noszticzius Z Amemiya T Ohmori T Yamaguchi T 《Chaos (Woodbury, N.Y.)》1999,9(2):283-297
The polarization curve of an acid-base interface in a hydrogel medium has a diode characteristic. Two of each such electrolyte diodes can be combined to give an electrolyte transistor. When a salt is added to the alkaline or to the acidic part of a reverse biased electrolyte diode, the current response is highly nonlinear. If the salt is added to the acidic side, even bistability can be observed. This bistability can generate complex oscillations in a base-acid-base electrolyte transistor. These nonlinear effects are studied experimentally and theoretically. While the nonlinear salt effect can be explained with the Nernst-Planck equations, to understand the bistable behavior further investigations are necessary. (c) 1999 American Institute of Physics. 相似文献
10.
Hegedus LS Greenberg MM Wendling JJ Bullock JP 《The Journal of organic chemistry》2003,68(11):4179-4188
Several dioxocyclams containing quinoxaline moieties, as well as their nickel(II) complexes were synthesized and studied for their ability to bind and oxidatively cleave DNA. Although no evidence for binding by intercalation was found, the ability of the Ni(II) complexes to cleave DNA in the presence of Oxone was strongly dependent on both the nature and the spatial orientation of the quinoxaline moieties, suggesting at least transient association of these complexes with DNA. 相似文献