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Air-stable P-chiral dihydrobenzooxaphosphole oxazoline ligands were designed and synthesized. When they were used in the iridium-catalyzed asymmetric hydrogenation of unfunctionalized 1-aryl-3,4-dihydronaphthalenes under one atmosphere pressure of H2, up to 99:1 e.r. was obtained. High enantioselectivities were also observed in the reduction of the exocyclic imine derivatives of 1-tetralones.

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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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An improved process using chiral hydrogenation is described for the synthesis in high yields of a 4-protected-(S)-piperazine-2-tert-butylcarboxaimide, an intermediate for an HIV protease inhibitor.

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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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Several polystyrene-supported proline dipeptides and a prolinamide derivative were prepared by thiol-ene coupling. These materials were used as catalysts for the direct asymmetric aldol reaction in water, and results compared with unsupported catalysts in water. Such an approach gave more active or stereoselective catalysts compared to the unsupported compounds, showing that our immobilization procedure may be useful to develop catalytic materials with enhanced performance. Moreover, these catalysts can be recovered and reused for at least nine times without loss of activity or can be easily regenerated when their activity has decreased.

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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 new method of synthesis of 2-(Z-1,2-diferrocenylvinyl)-4,5-dihydrooxazoles 3a-f and 5, 2-(Z-1,2-diferrocenylvinyl)-4,5-dihydrooxazol-3-ium salts 4a-f, 4g,h, and 9h-j by reactions of 2,3-diferrocenylcyclopropenylium salts 1a,b with 1,2-amino- and 1,2-N-alkylaminoalcohols in the presence of Et3N is described. The interactions of the salts 4a,d,f and 9h-j with morpholine and piperidine results in the corresponding (E)-2-[(N-2?,3?-diferrocenylacryloyl-2-(N-alkyl)amino]ethylmorpholines and piperidines. The characterization of the new compounds was done by IR, 1H and 13C NMR spectroscopy, mass-spectrometry, elemental analysis, and X-ray diffraction studies. Electrochemical properties of the compounds 3a-d and 4a-d were investigated using cyclic square voltammetry. One adsorption process and two electrochemical processes II and III, attributed to the oxidations of the ferrocene moieties, E0?(II), E0?(III), and comproportionation constant Kcom are reported.

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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 HIV-1 protease is a validated drug target for the design of antiretroviral drugs to combat AIDS. We previously established the sulfoximine functionality as a valid transition state mimetic (TSM) in the HIV-1 protease inhibitors (PI) design and have identified a lead pseudosymmetric compound with nanomolar enzymatic inhibitory activity. Here, we report the asymmetric synthesis of this compound and its application in the synthesis of sulfoximine-based peptidomimetic HIV-1 protease inhibitors. Molecular modeling revealed the potential mode of binding of the sulfoximine inhibitor as a TSM. The predicted absolute binding free energies suggested similar inhibitory effect as observed in our enzymatic inhibitory studies.

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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 stereodynamic probe for determination of the absolute configuration and enantiomeric composition of chiral amines, diamines, amino alcohols, amino acids, and alpha-hydroxy carboxylic acids is described. The chirality sensing is based on spontaneous asymmetric transformation of the first kind with stereolabile binaphtholate boron and zinc complexes. The substrate binding and chiral amplification processes yield a distinctive chiroptical sensor output at high wavelength that can be used for rapid and accurate ee detection of minute sample amounts.

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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 enantiorecognition of 1-aminoindane 3 and cis-1-amino-2-indanol 2 by (R,R)-alpha,alpha?-bis(trifluoromethyl)-9,10-anthracenedimethanol 1 is reported. The examination of the bidentate associations between 1 and 2 revealed that the cisoid conformation of 1 is responsible for the separation of the NMR signals. Two types of bimodal associations resulted from a cisoid conformation when meso-1 isomer was tested. Molecular mechanics modelling studies gave the possible structures of the associate species.

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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 present invention provides a compound represented by the formula wherein each symbol is as defined in the specification, or a salt thereof. The compound of the present invention shows a strong IAP antagonistic activity.

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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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In this report, the rapid syntheses of 24 novel C2-symmetric HIV-1 protease inhibitors are described. Two ortho-iodobenzyloxy containing C-terminal duplicated inhibitors served as starting materials for microwave-enhanced palladium(0)-catalyzed carbon-carbon bond forming reactions (Suzuki, Sonogashira, Heck, and Negishi). Highly potent inhibitors equipped with ortho-functionalized P1/P1? side chains as the structural theme were identified. Computational efforts were applied to study the binding mode of this class of inhibitors and to establish structure-activity relationships. The overall orientation of the inhibitors in the active site was reproduced by docking which suggested three possible conformations of the P1/P1? groups of which two seem more plausible.

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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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Base-functionalized aza-bis(oxazoline) ligands were prepared to explore the concept of dual activation through the Lewis acid and a tethered tertiary amine base. The catalytic activity of the Cu complex was evaluated for the asymmetric Henry reaction. Compared with a corresponding unfunctionalized copper complex with external 1-benzyl-4-ethylpiperazine base, the ethylpiperazine- functionalized aza-bis(oxazoline) copper catalyst resulted in rate acceleration (2.5 times) as well as improved enantioselectivity (72% ee vs 92% 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