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1.
Stereoselectivity in the intermolecular Pauson-Khand reaction of electron-deficient terminal alkynes
A family of terminal alkyne dicobalthexacarbonyl complexes bearing groups with a range of electron-withdrawing abilities has been synthesized. After submitting these complexes to the intermolecular Pauson-Khand reaction with norbornadiene, electron-deficient substrates afforded up to 26% of the unexpected endo-cyclopentenone. 相似文献
2.
Marcinkiewicz–Zygmund inequalities 总被引:1,自引:1,他引:0
We study a generalization of the classical Marcinkiewicz–Zygmund inequalities. We relate this problem to the sampling sequences in the Paley–Wiener space and by using this analogy we give sharp necessary and sufficient computable conditions for a family of points to satisfy the Marcinkiewicz–Zygmund inequalities. 相似文献
3.
N-Alkyl-N-nitrosoamides, RCON(NO)R′, react with primary aliphatic amines (NH2R″), in refluxing dichloromethane or at room temperature, to give RCONHR″ in 65–98% yields. 相似文献
4.
Paital AR Mitra T Ray D Wong WT Ribas-Ariño J Novoa JJ Ribas J Aromí G 《Chemical communications (Cambridge, England)》2005,(41):5172-5174
Based on a combined theoretical-experimental study, we propose that substituted m-phenylene ligands (m-N-Phi-N) can act as tuneable strong ferromagnetic couplers connecting Cu(II) ions; a new complex presenting that bridge with J close to +15 cm(-1) has been suggested and synthesized. 相似文献
5.
Jordi Faraudo Alex Travesset 《Colloids and surfaces. A, Physicochemical and engineering aspects》2007,300(3):287-292
In this paper, we argue that many of the fascinating electrostatic effects that take place in amphiphilic systems are strongly related to the particular organization of the oxygen atoms within each individual molecule. In particular, we focus on two effects: charge inversion and dielectric overscreening. For that purpose, we present molecular dynamics simulations of phosphatidic acid (DMPA2−) in the presence of divalent counterions. Our results show that the many oxygens present in DMPA2− cooperatively create strong binding sites for counterions, which in some cases lead to charge inversion. We also present an analysis of the role of interfacial water and relate our analysis to the phenomenon of dielectric overscreening. Several experimental implications are discussed in the conclusions. 相似文献
6.
Quantum mechanical and quantum mechanical/molecular mechanical calculations in conjunction with continuum solvation models have been used to analyze CH-pi interactions in model systems of aryl- and alkyl-aromatic interactions, as well as in a model folding system designed to study those interactions. High level calculations reproduced accurately the interaction of CH-pi interactions in both alkyl- and aryl-based model systems. Dispersion effects dominate the interaction, but the electrostatics term is also relevant for aryl CH-pi interactions. Theoretical calculations were also used to examine the influence of CH-pi interactions in determining the conformational flexibility of folding models. Finally, a critical comparison of the results obtained from high level calculations on model systems and the experimental data derived for folding models in apolar solvents was carried out, which allowed us to reconcile the apparent discrepancy found between both data. 相似文献
7.
New spin-state-selective (S3) NMR pulse sequences exclusively applying cross-polarization schemes to achieve optimum homonuclear and heteronuclear 1H-X coherence transfer are reported for the simple and accurate measurement of the magnitude and sign of heteronuclear coupling constants for samples at natural abundance. The proposed spin-edited HCP-TOCSY experiments are based on clean heteronuclear S3 excitation, generated by simultaneous co-addition of two independent in-phase and anti-phase components created during the mixing heteronuclear J-cross-polarization (HCP) step, which is finally transferred to other protons by a conventional homonuclear TOCSY mechanism. Selective 1D and non-selective 2D approaches for the easy determination of long-range proton-carbon and proton-nitrogen coupling constants on any protonated and non-protonated heteronuclei are presented and discussed for several organic molecules. 相似文献
8.
Elena Laukhina Vladislava Tkacheva Salavat Khasanov Leokadia Zorina Jordi Gómez-Segura Angel Pérez del Pino Jaume Veciana Vladimir Laukhin Concepció Rovira 《Chemphyschem》2006,7(4):920-923
Temperature has great impact on the structure and size of the linked crystallites of the conducting topmost layer formed at the surface of a polycarbonate film via the reaction BEDT-TTF+IBr [BEDT-TTF=bis(ethylenedithio)tetrathiafulvalene]. We show that fine temperature control permits formation of a semiconducting topmost layer of alpha'-(BEDT-TTF)(2)(I(x)Br(1-x))(3) crystallites with either micro- or nanometre size, a result that opens a route to miniaturized conducting plastic materials. 相似文献
9.
Pizarro N Llebaria A Cano S Joglar J Farré M Segura J de la Torre R 《Rapid communications in mass spectrometry : RCM》2003,17(4):330-336
3,4-Methylenedioxymethamphetamine (MDMA, ecstasy) is consumed as the racemate but some metabolic steps are enantioselective. In addition, chiral properties are preserved during MDMA biotransformation. A quantitative analytical methodology using gas chromatography/mass spectrometry (GC/MS) to determine enantioselective disposition in the body of MDMA and its main metabolites including 3,4-methylenedioxyamphetamine (MDA), 4-hydroxy-3-methoxymethamphetamine (HMMA), and 4-hydroxy-3-methoxyamphetamine (HMA) was developed. Plasma and urine samples were collected from a male volunteer. The analysis of MDMA, MDA, and 4-hydroxy-3-methoxy metabolites by GC/MS required a two-step derivatization procedure. The first step consisted of derivatization of the amine with enantiomerically pure Mosher's reagent ((R)-MTPCl). Triethylamine was used as a base to neutralize hydrochloric acid formed during the reaction allowing quantitative derivatization, which resulted in a substantial improvement in the sensitivity of the method compared with other previously described techniques. Further treatment with ammonium hydroxide was required since both amine and hydroxyl groups underwent derivatization in the reaction. Ammonium hydroxide breaks bonds formed with hydroxyl groups without affecting amine derivatives. The second derivatization step using hexamethyldisilazane was needed for metabolites containing phenol residues. This derivatization method permitted the stereochemically specific study of MDMA and its main monohydroxylated metabolites by GC/MS. A detailed study of the chemical reactions involved in the derivatization steps was indispensable to develop a straightforward, sensitive, and reproducible method for the analysis of the parent drug compound and its metabolites. 相似文献
10.
A method for the identification of double bond locations in polyunsaturated long chain alkenones adapted to nanogram amounts
as currently analyzed by gas chromatography coupled to mass spectrometry (GC-MS) has been developed. The method is based on
interpretation of the electron impact mass spectra of the imino derivatives of the carbonyl groups using either cyclopentyl
or phenyl substitutents. Other complementary derivatization methods such as elaidization and hydrogenation have also been
used for structural characterization of these compounds. This application has led to the identification of a novel homologous
series of di-, tri-, and tetraunsaturated ketones with carbon number chain lengths between 37 and 40 in coastal hypersaline
sediments. The novel series identified shows a distribution in which the double bond position between different homologs is
established by reference to the distance from the carbonyl group whereas the previously known alkenones were constituted by
unsaturated homologs with double bonds located at defined distances of the terminal methyl. This difference points out to
a dissimilar, but still unknown, biogenic precursor of these novel alkenones. 相似文献