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271.
Efficient Synthesis of Diaryl Ketones by Nickel‐Catalyzed Negishi Cross‐Coupling of Amides by Carbon–Nitrogen Bond Cleavage at Room Temperature Accelerated by a Solvent Effect
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Shicheng Shi Prof. Dr. Michal Szostak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(30):10420-10424
The first Negishi cross‐coupling of amides for the synthesis of versatile diaryl ketones by selective C?N bond activation under exceedingly mild conditions is reported. The cross‐coupling was accomplished with bench‐stable, inexpensive precatalyst [Ni(PPh3)2Cl2] that shows high functional‐group tolerance and enables the synthesis of highly functionalized diaryl ketone motifs. The coupling occurred with excellent chemoselectivity favoring the ketone (cf. biaryl) products. Notably, this process represents the mildest conditions for amide N?C bond activation accomplished to date (room temperature, <10 min). Considering the versatile role of polyfunctional biaryl ketone linchpins in modern organic synthesis, availability, and excellent functional‐group tolerance of organozinc reagents, this strategy provides a new platform for amide N?C bond/organozinc cross‐coupling under mild conditions. 相似文献
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Prof. Dr. Antonín Klásek Assoc. Prof. Dr. Stanislav Kafka Dr. Ondřej Rudolf Prof. Dr. Antonín Lyčka Dr. Michal Rouchal Lukáš Bednář 《ChemistryOpen》2021,10(6):645-652
3-Chloroquinoline-2,4-diones react with cyanide ions in dimethyl formamide to give 3-cyanoquinoline-2,4-diones in small yields due to the strong hindrance of the substituent at the C-3 atom. Good yields can be achieved if the substituent at this position is the methyl group. In the methanol solution, the reaction proceeds by an addition mechanism to form 2-oxo-1a,2,3,7b-tetrahydrooxireno[2,3-c]quinoline-7b-carbonitriles, from which 4-hydroxy-3-methoxy-2-oxo-1,2,3,4-tetrahydroquinoline-4-carbonitriles are subsequently formed by opening of the epoxide ring with methanol. Some minor products of these reactions have also been isolated. The 1H, 13C and 15N NMR spectra of the prepared compounds were measured, and all resonances were assigned using appropriate two-dimensional spectra. 相似文献
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Uzi Eliav Jonathan Gottesman Michal Wilk Uri Nevo 《Journal of Polymer Science.Polymer Physics》2015,53(22):1620-1628
Synthetic and biological gels undergo a sharp volume phase transition when subjected to a variety of environmental changes. Water and ion dynamics within swollen and compact phases are critical for understanding fundamental concepts in cellular (specifically neuronal) biophysics, for models of bound, free, or ordered water in complex environments; and for practical applications such as the design of gels for drug release, biomimetics, sensors, or actuators. In this work, we find, for the first time, basic physical parameters that shed light on the interaction of gels with water and electrolytes, across a volume phase transition. Water within a gel can be separated into bound and free populations with high exchange rate. We show that free water dynamics in compact gels are the same as those in pure water. Bound water was found to comprise a single layer around the polymers in both phases, with a correlation time three orders of magnitude higher than that of free water. Most importantly, salt‐induced phase transition was found to be different from a standard coil‐globule transition (e.g., temperature‐induced), with no rejection of bound water as the gel compacts. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1620–1628 相似文献
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Molecular dynamics (MD) simulations at normal and high temperature were used to study the flexibility and malleability of three microsomal cytochromes P450 (CYPs): CYP3A4, CYP2C9, and CYP2A6. Comparison of B-factors (describing the atomic fluctuations) between X-ray and MD data shows that the X-ray B-factors are significantly lower in the regions where the crystal contacts occur than for other regions. Consequently, the conclusions about CYP flexibility based solely on the X-ray data might be misleading. Comparison of flexibility patterns of the three CYPs enabled common features and variations in flexibility and malleability of the studied CYPs to be identified. The previously described pattern of flexibility in topological elements of microsomal CYPs (a rigid heme binding core, a malleable distal side and intermediately flexible proximal side) was confirmed. These topological features provide an important combination of high stereo- and regio-specificity (mediated by the relative rigidity in the neighborhood of the heme), together with high substrate promiscuity due to the more flexible active site and the malleability of the distal side. The data acquired here show that the malleability of the three studied CYPs correlates with their substrate specificity: CYP2A6 has a narrow substrate range and is the most rigid, CYP3A4 is the most promiscuous CYP known and is the most malleable, and CYP2C9 is intermediate in terms of both its substrate specificity and malleability. Thus, the malleability of CYPs is probably a major determinant of their substrate specificity. 相似文献
278.
Wujec M Siwek A Dzierzawska J Rostkowski M Kaminski R Paneth P 《The journal of physical chemistry. B》2008,112(39):12414-12419
The influence of the implicit solvent model on transition state structures of two S N2 reactions of biochemical importance is presented. In the considered methyl transfer reaction, we show experimentally that the rate constant in blood serum is about 60% slower than in the aqueous solution and that the implicit solvent model with slightly modified parameters for water captures correctly the energetics of this reaction. With the example of the reaction between 4-methyl-1,2,4-triazol-3-thione and ethyl bromoacetate, we show that relative stabilities of the conformationally different transition states depend upon the solvent inclusion strategy. 相似文献
279.
Ligor M Jarmalaviciene R Szumski M Maruska A Buszewski B 《Journal of separation science》2008,31(14):2707-2713
The aim of the investigations was to develop analytical methods for the determination of selected volatile and non-volatile organic compounds numbering among the final products of milk fermentation. The analyzed compounds were as follows: biacetyl and carboxylic acids (formic, acetic, citric, and lactic). The model yogurt was prepared under controlled conditions in our laboratory by addition of the selected bacteria (Lactobacillus bulgaricus and Streptococcus thermophilus) to the milk sample. The temperature, time, and stirring were controlled during the fermentation process. Factors considered in SPMPE-GC-FID method development included fiber exposure time, salt addition, temperature of extraction, and temperature of desorption. Various SPME fibers, for example with PDMS, CAR/PDMS, PA, and PDMS/DVB coatings, were tested to obtain the highest recovery of the investigated compounds extracted from yogurt samples. Based on these preliminary experiments, qualitative and quantitative analyses for the determination of biacetyl were performed by SPME-GC-FID. Moreover, a capillary zone electrophoresis method was developed for the determination of carboxylic acids in the yogurt samples. The buffer composition as well as deproteinization by acetonitrile were found to have a crucial effect on the analysis. 相似文献
280.
Poterya V Fárník M Oncák M Slavícek P 《Physical chemistry chemical physics : PCCP》2008,10(32):4835-4842
The photolysis of (H(2)O)(n) nanoparticles of various mean sizes between 85 and 670 has been studied in a molecular beam experiment. At the dissociation wavelength 243 nm (5.10 eV), a two-photon absorption leads to H-atom production. The measured kinetic energy distributions of H-fragments exhibit a peak of slow fragments below 0.4 eV with maximum at approximately 0.05 eV, and a tail of faster fragments extending to 1.5 eV. The dependence on the cluster size suggests that the former fragments originate from the photodissociation of an H(2)O molecule in the cluster interior leading to the H-fragment caging and eventually generation of a hydronium H(3)O molecule. The photolysis of surface molecules yields the faster fragments. At 193 nm (6.42 eV) a single photon process leads to a small signal from molecules directly photolyzed on the cluster surface. The two photon processes at this wavelength may lead to cluster ionization competing with its photodissociation, as suggested by the lack of H-fragment signal increase. The experimental findings are complemented by theoretical calculations. 相似文献