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Distribution coefficients of silver(1) complexes of pyridine derivatives have been determined potentiometrically by simultaneous measurement of and .All measurements were run at 25 +/- 0.1 deg C at an ionic strength Iota = 0.5 (KNO3).The knowledge of the distribution coefficients of particular complexes enables to determine magnitudes characterizing the extraction systems, such as extraction coefficient and percentage of extraction.

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

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A surprising example of enantioselective cascade Michael-oxa-Michael- tautomerization reactions of malononitrile and benzylidenechromanones has been developed. In this case, malononitrile functions as both nucleophile and electrophile. Meanwhile, a simple bifunctional indane amine-thiourea catalyst has been discovered to promote this process to afford high yields (up to 99%) and high to excellent enantiomeric excesses (81-99% ee). Copyright

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

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The heterogeneous catalytic oxidation of pyridines to pyridine N-oxides has been studied using tungsten-loaded TiO2as the catalyst and hydrogen peroxide as the green oxidant. The catalysts were synthesized by a simple impregnation technique and characterized by X-ray powder diffraction, Raman spectroscopy, transmission electron microscopy, energy dispersion X-ray spectroscopy, X-ray photoelectron spectroscopy. The catalytic performances of the catalysts were evaluated by the N-oxidation of pyridines with 30 wt% H2O2solution as an environmentally friendly oxidant at room temperature. These processes serve as an efficient method to prepare a variety of pyridine-N-oxides in modest to high yields, and the pyridine N-oxides could be easily separated from the heterogeneous catalytic system. This study will provide a useful strategy for preparation of heterocyclic N-oxides in the mild condition.

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

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A method for the direct methylation of aryl, heteroaryl, and vinyl boronate esters is reported, involving the reaction of iodomethane with aryl-, heteroaryl-, and vinylboronate esters catalyzed by palladium and PtBu2Me. This transformation occurs with a remarkably broad scope and is suitable for late-stage derivatization of biologically active compounds via the boronate esters. The unique capabilities of this method are demonstrated by combining carbon-boron bond-forming reactions with palladium-catalyzed methylation in a tandem transformation.

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

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The ion mobility techniques, including the most commonly used drift-tube ion mobility spectrometry (IMS) and differential mobility spectrometry (DMS), are used successfully for the detection of a wide range of organic compounds in the gas phase. In order to improve detection quality, admixtures are added to gas streams flowing through the detector. Dopants mostly prevent the ionization of interfering chemicals however, better detection may be also achieved by shifting the peaks in the drift-time spectra, enabling ionization of analytes with low proton affinities and, thus, facilitating photoionization. Fundamental information about ion-molecule reactions including the role of dopants is presented. The term ‘gas modifiers’ refers to substances that influence the ion transport by changing the mobility of ions without changing the chemistry of the ionization. The mechanism of the gas modifier’s interaction with an analyte in ion separation in drift tube IMS and DMS is explained in this paper.

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

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A scale of solute hydrogen-bond basicity has been set up using log K values for the complexation of a series of bases (i) against a number of reference acids in dilute solution in tetrachloromethane, equation (i). log Ki = LA log KBH + DA (i) Thirty-four such linear equations have been solved to yield 1, and 0, values that characterise the acids, and log KBH values that characterise the base; all the thirty-four equations intersect at a point where log K = -1.1 with K on the molar scale. This primary set of log Kz values involved 215 bases, and through a large number of secondary values we have been able to determine log KBH for some 500 bases, that include nearly all the functional groups encountered in organic chemistry. By making use of the ‘magic point,’ we have transformed log KBH into an entirely equivalent, but more convenient, scale through equation (ii). beta2H = (log KBH + 1.1)/4.636 (ii) Since we can take beta2H = 0 for all non-basic compounds such as alkanes and cycloalkanes, the new beta2H; hydrogen-bond solute basicity scale covers virtually all classes of base. We show that beta2H is not generally related to measures of full proton-transfer basicity such as aqueous pK or gaseous proton affinity (Epa) values, although family dependence is observed, and we stress that solute hydrogen-bond basicity must not be equated with full proton-transfer basicity. We also briefly investigate the solvent dependence of the beta2H values in terms of the Maria-Gal theta value, and we point out a number of exclusions to the ‘reasonably general’ beta2H scale

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

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The preparation, properties, and catalytic activity for new cationic rhodium(I) complexes of the general formulae left bracket Rh(NBD)L//2 right bracket ClO//4 and left bracket Rh(NBD)L(Pr//3) right bracket ClO//4 (NBD EQUVLNT 2,5-norbornadiene; L EQUVLNT nitrogen donor ligand; PR//3 EQUVLNT triarylphosphine) are described.

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

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The invention relates to a novel one pot method asymmetric synthesis process of a (S)-6-chlorine-4-cylopropyl ethylnen-4-trifluoromethyl-1,4-dihydro-2H-1,3-benzoxazine-2-ketone (Efavirenz) compound, the compound can be used as an reverse transcriptase inhibitor for human immunodeficiency virus (HIV). The invention also relates to a novel aminoalcohol ligand used for the process.

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

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Novel spirobis(oxazolines) provide excellent levels of stereocontrol in copper-catalysed Diels-Alder reactions; the larger the ligand bite angle the higher the enantioselection (up to 98.4% ee).

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

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We have developed a computer program (CRYSS), which may be used to rank the performance of a series of crystallization experiments. The method, at its simplest, allows the chemist to take composition data from partially purified crystallized solids and mother liquors; when this is coupled with initial composition data, the program can predict the maximum yield the system is capable of delivering after optimization. In this paper the underlying theoretical basis of the method is investigated by means of the crystallization of a three-component blend of hydrobenzoin isomers, along with the investigation of a four-component system based on aminoindanol. In the latter case, the modulation of purification performance via salt formation is demonstrated.

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