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排序方式: 共有200条查询结果,搜索用时 15 毫秒
1.
Gary H. Posner Timothy P. Kogan Stephen R. Haines Leah L. Frye 《Tetrahedron letters》1984,25(25):2627-2630
A short, reliable, and practical synthesis of ()-(+)-2-(-tolylsulfinyl)-2-buten-4-olide has been developed, and the utility of this Michael acceptor for highly enantiocontrolled synthesis of 3-substituted 4-butanolides has been demonstrated. 相似文献
2.
Appelhans LN Zuccaccia D Kovacevic A Chianese AR Miecznikowski JR Macchioni A Clot E Eisenstein O Crabtree RH 《Journal of the American Chemical Society》2005,127(46):16299-16311
Changing the counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)2 to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir(III) to give Ir(V) with little anion dependence. The N path, in contrast, goes by heterolytic C-H activation with proton transfer to the adjacent hydride. The proton that is transferred is accompanied by the counteranion in an anion-coupled proton transfer, leading to an anion dependence of the N path, and therefore of the N/AN selectivity. The N path goes via Ir(III), not Ir(V), because the normal NHC is a much less strong donor ligand than the abnormal NHC. PGSE NMR experiments support the formation of ion-pair in both the reactants and the products. 19F,1H-HOESY NMR experiments indicate an ion-pair structure for the products that is consistent with the computational prediction (ONIOM(B3PW91/UFF)). 相似文献
3.
Vera A. Vil' Yana A. Barsegyan Leah Kuhn Maria V. Ekimova Egor A. Semenov Alexander A. Korlyukov Alexander O. Terent'ev Igor V. Alabugin 《Chemical science》2020,11(20):5313
How far can we push the limits in removing stereoelectronic protection from an unstable intermediate? We address this question by exploring the interplay between the primary and secondary stereoelectronic effects in the Baeyer–Villiger (BV) rearrangement by experimental and computational studies of γ-OR-substituted γ-peroxylactones, the previously elusive non-strained Criegee intermediates (CI). These new cyclic peroxides were synthesized by the peroxidation of γ-ketoesters followed by in situ cyclization using a BF3·Et2O/H2O2 system. Although the primary effect (alignment of the migrating C–Rm bond with the breaking O–O bond) is active in the 6-membered ring, weakening of the secondary effect (donation from the OR lone pair to the breaking C–Rm bond) provides sufficient kinetic stabilization to allow the formation and isolation of stable γ-hydroperoxy-γ-peroxylactones with a methyl-substituent in the C6-position. Furthermore, supplementary protection is also provided by reactant stabilization originating from two new stereoelectronic factors, both identified and quantified for the first time in the present work. First, an unexpected boat preference in the γ-hydroperoxy-γ-peroxylactones weakens the primary stereoelectronic effects and introduces a ∼2 kcal mol−1 Curtin–Hammett penalty for reacquiring the more reactive chair conformation. Second, activation of the secondary stereoelectronic effect in the TS comes with a ∼2–3 kcal mol−1 penalty for giving up the exo-anomeric stabilization in the 6-membered Criegee intermediate. Together, the three new stereoelectronic factors (inverse α-effect, misalignment of reacting bonds in the boat conformation, and the exo-anomeric effect) illustrate the richness of stereoelectronic patterns in peroxide chemistry and provide experimentally significant kinetic stabilization to this new class of bisperoxides. Furthermore, mild reduction of γ-hydroperoxy-γ-peroxylactone with Ph3P produced an isolable γ-hydroxy-γ-peroxylactone, the first example of a structurally unencumbered CI where neither the primary nor the secondary stereoelectronic effect are impeded. Although this compound is relatively unstable, it does not undergo the BV reaction and instead follows a new mode of reactivity for the CI – a ring-opening process.Protecting stereoelectronic effects prevent Baeyer–Villiger rearrangement and stabilize γ-OX-γ-peroxylactones (X = H, OH), the previously elusive non-strained Criegee intermediates. 相似文献
4.
A conventional ion-exchange amino acid analyser kit has been simply and economically constructed for use with existing high-performance liquid chromatography (HPLC) apparatus. Sequential elution conditions are fully programmable by virtue of a 32K BBC microcomputer interfaced with an elution buffer selection valve and a thermostatically controlled column. Post-column derivatization with o-phthaladehyde-2-mercaptoethanol reagent enables fluorimetric detection at the picomole level. The system enables sensitive amino acid analysis of complex mixtures to be carried out by clinical and research laboratories who already possess HPLC apparatus but whose sample turnover does not merit purchase of a dedicated fully automated analyser. 相似文献
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6.
Verena Bögelein Frank Duzaar Leah Schätzler Christoph Scheven 《Journal of Differential Equations》2019,266(11):7709-7748
We establish that solutions to the Cauchy–Dirichlet problem for functionals of linear growth can be obtained as limits of solutions to flows with p-growth in the limit . The result can be interpreted on the one hand as a stability result. On the other hand it provides an existence result for general flows with linear growth. 相似文献
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8.
Saturation-transfer difference (STD)-NMR spectroscopy has been widely used to screen potential ligands for binding to large receptor molecules. The STD-NMR experiment is typically based on a proton NMR spectrum, which can suffer from spectral overlap, leading to missing information in STD-based epitope mapping. Two-dimensional STD-NMR experiments can alleviate spectral overlap, but are time consuming. Here, we examine the feasibility of saturating protons in a receptor molecule and observing the STD effect on nearby carbon nuclei after transferring polarization from protons to carbons using the insensitive nuclei enhanced by polarization transfer (INEPT) pulse sequence. We show that under favorable conditions, a 1H→13C STD-INEPT experiment can give information similar to that obtained from a two-dimensional heteronuclear experiment, but in significantly less time. The STD-INEPT experiment could be especially useful when studying mixtures of ligands in which the peak positions in the proton and HSQC spectrum change significantly, and in particular, when using high-throughput, automated methods to analyze the data. 相似文献
9.
Levi Evans Yiqui Shen Abigail Bender Leah E. Burnett Musheng Li Justine S. Habibian Tong Zhou Bradley S. Ferguson 《Molecules (Basel, Switzerland)》2021,26(5)
Plant-based foods, like fruits, vegetables, whole grains, legumes, nuts, seeds and other foodstuffs, have been deemed as heart healthy. The chemicals within these plant-based foods, i.e., phytochemicals, are credited with protecting the heart. However, the mechanistic actions of phytochemicals, which prevent clinical endpoints, such as pathological cardiac hypertrophy, are still being elucidated. We sought to characterize the overlapping and divergent mechanisms by which 18 selected phytochemicals prevent phenylephrine- and phorbol 12-myristate 13-acetate-mediated cardiomyocyte enlargement. Of the tested 18 compounds, six attenuated PE- and PMA-mediated enlargement of neonatal rat ventricular myocytes. Cell viability assays showed that apigenin, baicalein, berberine hydrochloride, emodin, luteolin and quercetin dihydrate did not reduce cell size through cytotoxicity. Four of the six phytochemicals, apigenin, baicalein, berberine hydrochloride and emodin, robustly inhibited stress-induced hypertrophy and were analyzed further against intracellular signaling and genome-wide changes in mRNA expression. The four phytochemicals differentially regulated mitogen-activated protein kinases and protein kinase D. RNA-sequencing further showed divergence in gene regulation, while pathway analysis demonstrated overlap in the regulation of inflammatory pathways. Combined, this study provided a comprehensive analysis of cardioprotective phytochemicals. These data highlight two defining observations: (1) that these compounds predominantly target divergent gene pathways within cardiac myocytes and (2) that regulation of overlapping signaling and gene pathways may be of particular importance for the anti-hypertrophic actions of these phytochemicals. Despite these new findings, future works investigating rodent models of heart failure are still needed to understand the roles for these compounds in the heart. 相似文献
10.
MRI of 54 patients with endometrial and cervical carcinoma was performed on a 0.6-T superconducting magnet. In 18 of 24 cases of surgically proved endometrial carcinoma, MRI accurately showed the depth of myometrial invasion. MRI was superior to CT scan for defining the primary site and extent of the tumor in 14 of 24 cases. Of 25 patients with cervical carcinoma studied, MRI was superior to CT scan in 15 of 19 cases with CT correlation for localizing the primary site. MRI showed parametrial extension and invasion of surrounding structures but is probably less reliable than CT scan for detection of adenopathy because of false positive findings from volume averaging with bowel. 相似文献