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A number of CF3-substituted carbinols decorated with an azine donor are efficiently prepared from fluoral and kinetically resolved in a reagent-controlled, Cu-H-catalysed Si-O coupling with a chiral silane. Selectivity factors are high, indicating a larger steric effect than CH 3 or C6H5 groups.

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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 cationic degradation product, formed in solution from retinal Schiff base (RSB), is examined in the gas phase using ion mobility spectrometry, photoisomerization action spectroscopy, and collision induced dissociation (CID). The degradation product is found to be N-n-butyl-2-(beta-ionylidene)-4-methylpyridinium (BIP) produced through 6pi electrocyclization of RSB followed by protonation and loss of dihydrogen. Ion mobility measurements show that BIP exists as trans and cis isomers that can be interconverted through buffer gas collisions and by exposure to light, with a maximum response at lambda = 420 nm. Graphical Abstract[Figure not available: see fulltext.]

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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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Arenastatin A (1, cryptophycin 24) was synthesized by convergence of hydroxy ester 16 with amino acid derivative 27; two independent and highly efficient routes to 16 are disclosed.

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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 CuII atom of the title complex, [Cu(C9H7NO3)-(C7H 9N)(H2O)], has a square-pyramidal coordination sphere with a tridentate N-salicylideneglycinato Schiff base dianion and a 2,4-dimethylpyridine ligand bound in the basal plane. The apex of the pyramid is occupied by an O atom from the coordinated water molecule at an apical distance of 2.416 (2) A. The monomeric moieties in the crystal are stabilized through hydrogen bonding, building a two-dimensional network. The copper(II) polyhedra are arranged in two magnetically inequivalent orientations, leading to a slightly distorted ferrodistortive coupled g tensor.

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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 efficient and regioselective introduction method of 2-methylpyridines to the secondary position of Baylis-Hillman adducts has been developed. A base treatment of 2-methylpyridinium salt of Baylis-Hillman bromide generated N-allylenamine intermediate which underwent a facile 3-aza-Cope rearrangement under mild conditions to produce the product.

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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 series of 1?-(6-aminopurin-9-yl)-1?-deoxy-N-methyl-beta-D-ribofuranuronamides that were characterised by 2-dialkylamino-7-methyloxazolo[4,5-b]pyridin-5-ylmethyl substituents on N6 of interest for screening as selective adenosine A3 receptor agonists, have been synthesised. This work involved the synthesis of 2-dialkylamino-5-aminomethyl-7-methyloxazolo[4,5-b]pyridines and analogues that were coupled with the known 1?-(6-chloropurin-9-yl)-1?-deoxy-N-methyl-beta-D-ribofuranuronamide. The oxazolo[4,5-b]pyridines were synthesized by regioselective functionalisation of 2,4-dimethylpyridine N-oxides. The regioselectivities of these reactions were found to depend upon the nature of the heterocycle with 2-dimethylamino-5,7-dimethyloxazolo[4,5-b]pyridine-N-oxide undergoing regioselective functionalisation at the 7-methyl group on reaction with trifluoroacetic anhydride in contrast to the reaction of 4,6-dimethyl-3-hydroxypyridine-N-oxide with acetic anhydride that resulted in functionalisation of the 6-methyl group. To optimise selectivity for the A3 receptor, 5-aminomethyl-7-bromo-2-dimethylamino-4-[(3-methylisoxazol-5-yl)methoxy]benzo[d]oxazole was synthesised and coupled with the 1?-(6-chloropurin-9-yl)-1?-deoxy-N-methyl-beta-D-ribofuranuronamide. The products were active as selective adenosine A3 agonists.

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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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Complexes of the type [Pt(L)Cl3]- (L = pyridine derivative) were synthesized and studied by 13C and 195Pt NMR spectroscopies. The 195Pt signals were observed between -1720 and -1897 ppm. No correlation between the delta(Pt) and the pKa of the protonated pyridine derivatives was found. The chemical shifts vary with the substituents on the pyridine ligand. Compounds with substituents in ortho positions were observed at lower fields, except for complexes containing hydroxy or amine groups. The latter compounds were observed at higher fields, close to the signals of the Pt-unsubstituted pyridine compound. These results were explained in terms of the solvent effect. The chemical shifts delta(C) and the coupling constants J(13C-195Pt) were measured and the results interpreted with a view of obtaining information on the nature of the Pt – N bond. The possibility of pi-bonding between platinum and the pyridine ligand is examined. The conformation of the pyridine ring in relation to the platinum plane and the energies of the rotation barriers around the Pt – N bond in these types of platinum(II) complexes are briefly discussed. The crystal structure of trans-Pt(2,6-(HOCH2)2py)2Cl2-2H 2-O was determined by X-ray diffraction. The compound is monoclinic, C2/m, a = 7.022(6), b = 15.646(13), c = 8.344(10) A, ss= 93.35(8), Z = 2, R = 0.037. The platinum atom is located at the junction of the twofold axis and the mirror plane, the N atoms and the para-C atom of the pyridine ring are situated on the twofold axis, and the chloride ligands are on the mirror plane. The compound crystallizes with molecules of water, which are H-bonded to the hydroxy groups. The Pt – Cl bond distance is 2.306(2) A, and that of the Pt – N bond is 2.041(6) A. The dihedral angle between the platinum and the pyridine planes is 79.8.

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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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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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Provided are a series of BTK inhibitors, and specifically disclosed are a compound, pharmaceutically acceptable salt thereof, tautomer thereof or prodrug thereof represented by formula (I), (II), (III) or (IV).

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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 the framework of our studies on acid-base equilibria in systems comprising substituted pyridines and nonaqueous solvents, acid dissociation constants have been determined potentiometrically for a variety of cationic acids conjugated with pyridine and its derivatives in the polar protophobic aprotic solvent nitromethane. The potentiometric method enabled a check as to whether and to what extent cationic homoconjugation equilibria of the BH+/B type, as well as cationic heteroconjugation equilibria in BH+/B1 systems without proton transfer, are set up in nitromethane. The equilibrium constants were compared with those determined in water and two other polar protophobic aprotic solvents, propylene carbonate and acetonitrile. The pKa values of acids conjugate to the N-bases in nitromethane fall in the pKa range of 5.84 to 17.67, i.e., 6 to 7 pKa units, on average, higher than in water, 1 to 2 units higher than in propylene carbonate, and less than 1 unit lower than in acetonitrile. This means that the basicity of the pyridine derivatives increases on going from propylene carbonate through nitromethane to acetonitrile. Further, it was found that the sequence of the pKa changes of the protonated amines was consistent in all three media, thus providing the basis for establishing linear correlations among these values. In the majority of the BH+/B systems in nitromethane, cationic homoconjugation equilibria have been established. The cationic homoconjugation constants, log KBHB+, are relatively low, falling in the range 1.60-2.89. A comparison of the homoconjugation constants in nitromethane with those in propylene carbonate and acetonitrile shows that nitromethane is a more favorable solvent for the cationic homoconjugation equilibria than the other two solvents. Moreover, results of the potentiometric measurements revealed that cationic heteroconjugation equilibria were not present in the majority of the BH+/B1 systems in nitromethane. The heteroconjugation constant could be determined in one system only, with log KBHB1+ = 2.56.

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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