Top Picks: new discover of 2,4-Dimethylpyridine

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Fe(PyTACN)-catalyzed cis-dihydroxylation of olefins with hydrogen peroxide

A family of iron complexes with general formula [Fe(II)( R,Y,XPyTACN)(CF3SO3)2], where R,Y,XPyTACN=1-[2?-(4-Y-6-X-pyridyl)methyl]-4,7-dialkyl-1,4, 7-triazacyclononane, X and Y refer to the groups at positions 4 and 6 of the pyridine, respectively, and R refers to the alkyl substitution at N-4 and N-7 of the triazacyclononane ring, are shown to be catalysts for efficient and selective alkene oxidation (epoxidation and cis-dihydroxylation) employing hydrogen peroxide as oxidant. Complex [Fe(II)(Me,Me,HPyTACN)(CF 3SO3)2] (7), was identified as the most efficient and selective cis-dihydroxylation catalyst among the family. The high activity of 7 allows the oxidation of alkenes to proceed rapidly (30 min) at room temperature and under conditions where the olefin is not used in large amounts but instead is the limiting reagent. In the presence of 3 mol% of 7, 2 equiv. of H2O2 as oxidant and 15 equiv. of water, in acetonitrile solution, alkenes are cis-dihydroxylated reaching yields that might be interesting for synthetic purposes. Competition experiments show that 7 exhibits preferential selectivity towards the oxidation of cis olefins over the trans analogues, and also affords better yields and high [syn-diol]/[epoxide] ratios when cis olefins are oxidized. For aliphatic substrates, reaction yields attained with the present system compare favourably with state of the art Fe-catalyzed cis-dihydroxylation systems, and it can be regarded as an attractive complement to the iron and manganese systems described recently and which show optimum activity against electron-deficient and aromatic olefins. Copyright

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Application of 108-47-4, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.108-47-4, Name is 2,4-Dimethylpyridine, molecular formula is C7H9N. In a article£¬once mentioned of 108-47-4

Low-voltage electrically-enhanced microextraction as a novel technique for simultaneous extraction of acidic and basic drugs from biological fluids

In the present work, for the first time a new set-up was presented for simultaneous extraction of acidic and basic drugs using a recent novel electrically-enhanced microextraction technique, termed electromembrane extraction at low voltages followed by high performance liquid chromatography with ultraviolet detection. Nalmefene (NAL) as a basic drug and diclofenac (DIC) as an acidic drug were extracted from 24mL aqueous sample solutions at neutral pH into 10muL of each acidified (HCl 50mM) and basic (NaOH 50mM) acceptor solution, respectively. Supported liquid membranes including 2-nitrophenyl octyl ether containing 5% di-(2-ethylhexyl) phosphate and 1-octanol were used to ensure efficient extraction of NAL and DIC, respectively. Low voltage of 40V was applied over the SLMs during 14min extraction time. The influences of fundamental parameters affecting the transport of target drugs were optimized using experimental design. Under optimal conditions, NAL and DIC were extracted with extraction recoveries of 12.5 and 14.6, respectively, which corresponded to preconcentration factors of 300 and 350, respectively. The proposed technique provided good linearity with correlation coefficient values higher than 0.9956 over a concentration range of 8-500mugL-1 and 12-500mugL-1 for NAL and DIC, respectively. Limits of detection and quantifications, and intra-day precisions (n=3) were less than 4mugL-1, 12mugL-1, and 10.1%, respectively. Extraction and determination of NAL and DIC in human urine samples were successfully performed. In light of the data obtained in the present work, this new set-up for EME with low voltages has a future potential as a simple, selective, and fast sample preparation technique for simultaneous extraction and determination of acidic and basic drugs in different complicated matrices.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Discovery of 2,4-Dimethylpyridine

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Design, Synthesis, and Evaluation of the Highly Selective and Potent G-Protein-Coupled Receptor Kinase 2 (GRK2) Inhibitor for the Potential Treatment of Heart Failure

A novel class of therapeutic drug candidates for heart failure, highly potent and selective GRK2 inhibitors, exhibit potentiation of beta-adrenergic signaling in vitro studies. Hydrazone derivative 5 and 1,2,4-triazole derivative 24a were identified as hit compounds by HTS. New scaffold generation and SAR studies of all parts resulted in a 4-methyl-1,2,4-triazole derivative with an N-benzylcarboxamide moiety with highly potent activity toward GRK2 and selectivity over other kinases. In terms of subtype selectivity, these compounds showed enough selectivity against GRK1, 5, 6, and 7 with almost equipotent inhibition to GRK3. Our medicinal chemistry efforts led to the discovery of 115h (GRK2 IC50 = 18 nM), which was obtained the cocrystal structure with human GRK2 and an inhibitor of GRK2 that potentiates beta-adrenergic receptor (betaAR)-mediated cAMP accumulation and prevents internalization of betaARs in beta2AR-expressing HEK293 cells treated with isoproterenol. Therefore, 115h appears to be a novel class of therapeutic for heart failure treatment.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Trifluoromethyl benzyl alcohol as a “shift reagent” in ion mobility spectrometry: The effect of intramolecular bridges, ion size and shift reagent-ion binding energy in ion mobility

alpha-Trifluoromethyl benzyl alcohol (F) was introduced as a “shift reagent” in the buffer gas of an electrospray ionization ion mobility spectrometer coupled to a quadrupole mass spectrometer to explain the mobility shifts of selected compounds; ion mobilities depended on ion sizes and F-ion adducts binding energies calculated using Gaussian 09 at the X3LYP/6-311++G(d,p) level. The mobility shifts with the introduction of F in the buffer gas were: – 13% (ethanolamine), – 10.6% (serine), – 8.6% (threonine), – 7.3% (phenylalanine), – 7.0% (tyrosine), – 6.2 (tributylamine), – 5.1% (valinol), – 4.7% (methionine), – 3.9% (tryptophan), – 3.1% (tribenzylamine), – 1.3% (2,6-di-tert-butyl pyridine, DTBP), – 1.2% (2,4-lutidine, 2,4-dimethyl pyridine), and – 0.1% (atenolol). These mobility shifts showed a decreasing trend with the increase in molecular weight from ethanolamine to tribenzylamine excluding some ions due to steric hindrance (2,4-lutidine, DTBP and tetraalkylammonium ions), formation of intramolecular bridges (atenolol and methionine) or low binding energy with F (valinol). Ethanolamine (61.1 g/mol) showed the largest mobility shift (- 13%) due to its low molecular weight and tribenzylamine showed the smallest one due to its large size. We found a similar trend in mobility shifts when methyl chloro propionate, trifluoromethyl benzyl alcohol, ethyl lactate, nitrobenzene or 2-butanol were used as SRs. We also found that penicillamine adducts with F were not seen in the mass or mobility spectra probably because of the formation of an intramolecular bridge in this compound; F produced the average lowest mobility shifts of all SRs tried before, even of smaller size (methyl chloro propionate, phenylethanol, ethyl lactate, nitrobenzene, and 2-butanol) because of the inductive effects exerted by the three fluorine atoms that decreased F proton affinity and hindered its adduction to analyte ions. In summary, intramolecular bridges, size, inductive effects, steric hindrance and adduct binding energy were used to explain mobility shifts when trifluoromethyl benzyl alcohol was used as a “shift reagent” in ion mobility spectrometry.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Mechanisms of Nickel-Catalyzed Coupling Reactions and Applications in Alkene Functionalization

ConspectusNickel complexes exhibit distinct properties from other group 10 metals, including a small nuclear radius, high paring energy, low electronegativity, and low redox potentials. These properties enable Ni catalysts to accommodate and stabilize paramagnetic intermediates, access radical pathways, and undergo slow beta-H elimination. Our research program investigates how each of these fundamental attributes impact the catalytic properties of Ni, in particular in the context of alkene functionalization.Alkenes are versatile functional groups, but stereoselective carbofunctionalization reactions of alkenes have been underdeveloped. This challenge may derive from the difficulty of controlling selectivity via traditional two-electron migratory insertion pathways. Ni catalysts could lead to different stereodetermining steps via radical mechanisms, allowing access to molecular scaffolds that are otherwise difficult to prepare. For example, an asymmetric alkene diarylation reaction developed by our group relies upon the radical properties of Ni(III) intermediates to control the enantioselectivity and give access to a library of chiral alpha,alpha,beta-triarylethane molecules with biological activity.Mechanistic studies on a two-component reductive 1,2-difunctionalization reaction have shed light on the origin of the cross-electrophile selectivity, as C sp2 and C sp3 electrophiles are independently activated at Ni(I) via two-electron and radical pathways, respectively. Catalyst reduction has been identified to be the turnover-limiting step in this system. A closer investigation of the radical formation step using a (Xantphos)Ni(I)Ar model complex reveals that Ni(I) initiates radical formation via a concerted halogen-abstraction pathway.The low redox potentials of Ni have allowed us to develop a reductive, trans-selective diene cyclization, wherein a classic two-electron mechanism operates on a Ni(I)/Ni(III) platform, accounting for the chemo- and stereoselectivity. This reaction has found applications in the efficient synthesis of pharmaceutically relevant molecules, such as 3,4-dimethylgababutin.The tendency of Ni to undergo one-electron redox processes prompted us to explore dinuclear Ni-mediated bond formations. These studies provide insight into Ni-Ni bonding and how two metal centers react cooperatively to promote C-C, C-X, and N-N bond forming reductive elimination.Finally, isolation of beta-agostic Ni and Pd complexes has allowed for X-ray and neutron diffraction characterization of these highly reactive molecules. The bonding parameters serve as unambiguous evidence for beta-agostic interactions and help rationalize the slower beta-H elimination at Ni relative to Pd. Overall, our research has elucidated the fundamental properties of Ni complexes in several contexts. Greater mechanistic understanding facilitates catalyst design and helps rationalize the reactivity and selectivity in Ni-catalyzed alkene functionalization reactions.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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SYNTHESIS AND PHARMACOLOGICAL ACTIVITY OF A PYRIDO<3',4':5,4>PYRROLO<1,2-c>–<1,4>BENZODIAZEPINE-3,10-DIONE, A NEW BENZODIAZEPINE-&beta-CARBOLINE TYPE HYBRID MOLECULE

Diethyl 2,3-dihydro-6-azaindoline-2,5-dicarboxylate 4b was synthesized and used as starting material in the preparation of a novel benzodiazepine-beta-carboline type hybrid molecule (3aR,S)-ethyl 3,10-dioxo-2,3,3a,4-tetrahydro-10H-pyrido<3',4':5,4>pyrrolo<1,2-c><1,4>-benzodiazepine-6-carboxylate 5b.The benzodiazepine receptor binding affinities of this compound and its precursors were found to be very modest in vitro.These results confirm our previously proposed model of the configuration of the benzodiazepine and beta-carboline binding sites on the receptor as represented by the configuration of these two moieties in the high affinity hybrid 3.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Some scientific research about 2,4-Dimethylpyridine

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Electric Literature of 108-47-4, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.108-47-4, Name is 2,4-Dimethylpyridine, molecular formula is C7H9N. In a Article£¬once mentioned of 108-47-4

A second order group contribution method for the prediction of critical temperatures and enthalpies of vaporization of organic compounds

A new method based on group contribution additivity, and using Benson’s second order groups, is proposed for the prediction of critical temperatures and enthalpies of vaporization of covalent compounds. Contributions for hydrocarbons and hydrocarbon derivatives containing oxygen, nitrogen, chlorine, bromine and/or sulphur, are given. Results are compared to predictions made using the most common existing first or second order group contribution methods. The overall precision for Tc predictions of 381 compounds is 5.8 K, compared to 23.6 K with the method of Joback and 9.2 K with the method of Constantinou. The precision for predicted DeltaHvap of 319 compounds, at 298 K and at the normal boiling point, is improved by a factor 2 when comparing to the results of the method of Svoboda. Furthermore, one single group decomposition may now be used for the computation of gas phase properties, Tc, and DeltaHvap at any temperature lower than T c, leading to liquid phase thermochemical functions with better precision and simplicity.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Top Picks: new discover of 108-47-4

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Calibration of the mobility scale in ion mobility spectrometry: The use of 2,4-lutidine as a chemical standard, the two-standard calibration method and the incorrect use of drift tube temperature for calibration

Ion mobility spectrometry (IMS) is an analytical technique that separates ions in the gas phase under the influence of an electric field according to their size to charge ratio. We used electrospray ionization IMS-quadrupole mass spectrometry to study the mobility shifts of 2,4-lutidine with temperature or the introduction of several contaminants in the drift gas. We found the reduced mobility (K0) of 2,4-lutidine to decrease up to 24% when contaminants were introduced into the drift gas. We also show the significant variation of 2,4-lutidine’s K0 with the drift tube temperature, 8.5% from 100 to 322 C. These changes in 2,4-lutidine’s mobility were due to variations in clustering by changes in temperature or contaminant concentration. This dependence of 2,4-lutidine’s K0 with temperature and contamination in the drift gas makes this chemical standard unsuitable to calibrate the mobility scale. Despite these findings, 2,4-lutidine is still used for this purpose. The shortcomings of the IMS two-standard calibration and the incorrect use of the drift tube temperature for calibration are also discussed. We suggest that accurate reduced mobilities must be determined for small ions only in a highly purified drift gas using calibrants with a well determined K0 such as di tert-butyl pyridine at high temperatures, where clustering is low, and the drift gas temperature is measured instead of the drift tube temperature.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 108-47-4, name is 2,4-Dimethylpyridine, introducing its new discovery. category: chiral-nitrogen-ligands

Simple derivatization method for sensitive determination of fatty acids with fluorescence detection by high-performance liquid chromatography using 9-(2-hydroxyethyl)-carbazole as derivatization reagent

A simple and sensitive method for the determination of short and long-chain fatty acids using high-performance liquid chromatography with fluorimetric detection has been developed. The fatty acids were derivatized to their corresponding esters with 9-(2-hydroxyethyl)-carbazole (HEC) in acetonitrile at 60C with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride as a coupling agent in the presence of 4-dimethylaminopyridine (DMAP). A mixture of esters of C1-C20 fatty acids was completely separated within 38 min in conjunction with a gradient elution on a reversed-phase C18 column. The maximum fluorescence emission for the derivatized fatty acids is at 365 nm (lambdaex 335 nm). Studies on derivatization conditions indicate that fatty acids react proceeded rapidly and smoothly with HEC in the presence of EDC and DMAP in acetonitrile to give the corresponding sensitively fluorescent derivatives. The application of this method to the analysis of long chain fatty acids in plasma is also investigated. The LC separation shows good selectivity and reproducibility for fatty acids derivatives. The R.S.D. (n = 6) for each fatty acid derivative are <4%. The detection limits are at 45-68 fmol levels for C14-C20 fatty acids and even lower levels for category: chiral-nitrogen-ligands

Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

More research is needed about (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Highly Enantioselective Aldol Reaction: Development of a New Chiral Auxiliary from cis-1-Amino-2-hydroxyindan

Boron enolates obtained from optically active oxazolidinone derivative of cis-1-amino-2-hydroxyindan are reacted with various aldehydes to provide highly enantioselective aldol products in good yields.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis