Brief introduction of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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We have successfully developed a series of novel and modular ferrorence-based amino-phosphine-alcohol (f-Amphol) ligands, and applied them to iridium-catalyzed asymmetric hydrogenation of various simple ketones to afford the corresponding chiral alcohols with excellent enantioselectivities and conversions (98?99.9 % ee, >99 % conversion, turnover number up to 200 000). Control experiments and density functional theory (DFT) calculations have shown that the hydroxyl group of our f-Amphol ligands played a key role in this asymmetric hydrogenation.

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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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Heats of ionization by thermometric titration for a series of bases (or acids) can be used to compare solid acids (or bases) with liquid analogues bearing the same functionalities in homogeneous solutions.The method is demonstrated for Broensted acids by reacting a series of substituted nitrogen bases with solutions of p-toluenesulfonic acid (PTSA) in acetonitrile and with suspensions of the microporous polymeric arylsulfonic acid resin-Dowex 50W-X8 in the same solvent.Under well-controlled anhydrous conditions there is a good correlation (r=0.992) between the heats of reaction of the bases with the homogeneous and heterogeneous acid systems, but the homogeneous system gives a more exothermic interaction by 3-4 kcal/mol for a series of 29 substituted pyridines, anilines, and some other amines.This difference may be attributed to homohydrogen bonding interactions between excess acid and sulfonate anion sites which are more restricted geometrically in the resin than in solution.Other factors which affect the enthalpy change for the acid-base interaction are the acid/base ratio, the water content of the sulfonic acid, the solvent, and the resin structure (e.g., microporous vs. macroporous).Steric hindrance in the base not differentiate solid from homogeneous acid.In addition to the use of titration calorimetry, heats of immersion are reported for the Dowex-arylsulfonic acid resins and the Nafion-perfluorinated sulfonic acid resin in a series of basic liquids.The results are compared with each other and with those from a previous study of several varieties of coal.

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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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Densities and viscosities of the binary mixtures (benzene or cyclohexane +2,4-lutidine, +2,6-lutidine, +collidine, +mesitylene, +m-xylene and +p-xylene) between 303.15 and 323.15 K over the whole range composition, were determined.Experimental results were fitted to the Grundberg and Nissan equation.The values obtained for the excess viscosities and the parameter delta of the Grundberg-Nissan equation can be explained in terms of the dipole moments of the compounds, the ?-electron structure of the aromatic molecules and the formation of electron donor-acceptor complexes.

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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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Chemical research careers are more diverse than they might first appear, as there are many different reasons to conduct research and many possible environments. category: chiral-nitrogen-ligands, Name is (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol, belongs to chiral-nitrogen-ligands compound, is a common compound. category: chiral-nitrogen-ligandsCatalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. In an article, authors is Wang, Bin, once mentioned the new application about category: chiral-nitrogen-ligands.

Bifunctional asymmetric phase-transfer catalysts bearing multiple hydrogen-bonding donors have rarely been explored. The first quaternary ammonium type of these catalysts derived from cinchona alkaloids were readily prepared and found to be highly efficient catalysts for asymmetric nitro-Mannich reactions of amidosulfones. Compared with previous reports, very broad substrate generality was observed, and both enantiomers of the products were achieved in high enantio- and diastereoselectivity (90-99% ee, 13:1 to 99:1 dr).

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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

Extracurricular laboratory:new discovery of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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A series of new chiral 6-substituted purinyl and 8-aza-purinyl carbonucleosides based on indanol were synthesized from the commercially available (1R,2S)-1-amino-2-indanol and (1S,2R)-1-amino-2-indanol based on a well-known methodology.

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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

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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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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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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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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