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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

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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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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

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FERROCENYLTRITHIOCARBONATES I. DIRECT ACCESS FROM alpha-FERROCENYLCARBINOLS BY A SNi MECHANISM. ABSOLUTE X-RAY STRUCTURE DETERMINATION OF (R)-FERROCENYLMETHYLMETHANE S-METHYLTRITHIOCARBONATE

Ferrocenyltrithiocarbonates (I) are readily obtained by treating alpha-ferrocenylcarbinols (II) successively with sodium hydride, carbon disulfide and alkyl halide.Formation of I occurs by intramolecular nucleophilic displacement of oxygen by sulfur with retention of configuration.This is supported by the nature of the other products formed and by the X-ray structure determination of an optically active compound I, which was refined to R = 0.038.The title compound of R configuration was obtained from (R)-ferrocenylmethylmethanol.

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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

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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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Contributions to the chemistry of silicon-sulfur compounds. 76. Zinc(II) tri-tert-butoxysilanethiolates. Synthesis, properties, crystal and molecular structures of [Zn{SSi(OBut)3}2(NH3)L] (L = 2-picoline or 2,4-lutidine) and [Zn{SSi(OBut)3}2(NH3)2] ¡¤ MeCN complexes

[Zn{SSi(OBut)3}2(NH3)]2 (1) reacts with 2-picoline or 2,4-lutidine (L) without elimination of ammonia giving stable monometallic complexes [Zn{SSi(OBut)3}2(NH3)L] (3 and 4), with two different nitrogen ligands bonded to the metal center. Reaction of (ButO)3SiSH with zinc di(acetylacetonate) in ammonia atmosphere leads to the complex with two ammine ligands [Zn{SSi(OBut)3}2(NH3)2] ¡¤ MeCN (5). Molecular and crystal structures of 3, 4 and 5 have been determined by the single crystal X-ray structural analysis. All have distorted tetrahedral geometry. The presence of ammonia gives rise to hydrogen bonds, different in all three cases. 3, 4, and 5 are the first examples of structurally characterized ammine ligated zinc thiolates. WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001.

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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

Awesome Chemistry Experiments For (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Visual enantiomeric recognition of amino acid derivatives in protic solvents

Various types of chiral host molecules 2-7 based on a phenolphthalein skeleton and two crown ethers were prepared for use in visual enantiomeric recognition, and we examined their enantioselective coloration in complexation with chiral amino acid derivatives 9-22 in methanol solution. Methyl-substituted host (S,S,S,S)-S showed particularly prominent enantiomer selectivity for the alanine amide derivatives 11 and 12. A combination of methyl-substituted host (S,S,S,S)-S with guest (R)-11 or (R)-12 developed a purple color, whereas no color development was observed with (S)-11 or (S)-12. On the other hand, phenyl-substituted host (S,S,S,S)-6 showed deeper coloration with a wide range of (S)-beta-amino alcohols compared to that seen with host (S,S,S,S)-6 and the corresponding (R)-beta-amino alcohols at 0C. Furthermore, absorbance inversion temperatures (AIT) were observed within the range of 0-50C in many cases.

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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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High-pressure accelerated asymmetric organocatalytic friedel-crafts alkylation of indoles with enones: Application to quaternary stereogenic centers construction

An organocatalytic Friedel-Crafts alkylation of indoles with alpha,beta-unsaturated ketones was found to be efficiently accelerated under high-pressure conditions with a low loading of chiral primary amine salts with good yield and enantioselectivity up to 90%. This approach also allows, for the first time, selected indole derivatives containing quaternary stereogenic centers to be obtained from prochiral beta,beta-disubstituted enones with an enantioselectivity up to 80%.

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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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Asymmetric synthesis of chiral organofluorine compounds: Use of nonracemic fluoroiodoacetic acid as a practical electrophile and its application to the synthesis of monofluoro hydroxyethylene dipeptide isosteres within a novel series of HIV protease inhibitors

Two stereoselective routes to a series of diastereomeric inhibitors of HIV protease, monofluorinated analogues of the Merck HIV protease inhibitor indinavir, are described. The two routes feature stereoselective construction of the fluorinated core subunits by asymmetric alkylation reactions. The first-generation syntheses were based on the conjugate addition of the lithium enolate derived-from pseudoephedrine alpha-fluoroacetamide to nitroalkene 12, a modestly diastereoselective transformation. A more practical second-generation synthetic route was developed that is based on a novel method for the asymmetric synthesis of organofluorine compounds, by enolate alkylation using optically active fluoroiodoacetic acid as the electrophile in combination with a chiral amide enolate. Resolution of fluoroiodoacetic acid with ephedrine provides either enantiomeric form of the electrophile in ?96% ee. Alkylation reactions with this stable and storable chiral fluorinated precursor are shown to proceed in a highly stereospecific manner. With the development of substrate-controlled syn- or anti-selective reductions of alpha-fluoro ketones 44 and 45 (diastereomeric ratios 12:1-84:1), efficient and stereoselective routes to each of the four targeted inhibitors were achieved. The optimized synthetic route to the most potent inhibitor (syn,syn-4, Ki = 2.0 nM) proceeded in seven steps (87% average yield per step) from aminoindanol hydrocinnamide 40 and (S)-fluoroiodoacetic acid, and allowed for the preparation of more than 1 g of this compound. The inhibition of HIV-1 protease by each of the fluorinated inhibitors was evaluated in vitro, and the variation of potency as a function of inhibitor stereochemistry is discussed.

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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