Interesting scientific research on (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Results are reported from molecular mechanics (MM), molecular dynamics (MD) and a combined mode – MD with a subsequent MM minimization, of the complexes of the chiral solvating agent (CSA) alpha,alpha?-bis(trifluoromethyl)-9,10-anthracenedimethanol (1) in two of its diastereoisomeric forms ((R,R)- and meso-) with the substrates (1S,2R)- and (1R,2S)-cis-1-amino-2-indanol (2). Our computational work was stimulated by preceding NMR study of the enantio differentiation capacity of the CSA manifested in the formation of bidentate complexes with the substrates. The molecular modeling and simulation studies gave possible structures and relative stabilities of the associated species. MM minimizations were sufficient in order to find the lowest energy minima of meso-1/(1S,2R)-2 and (R,R)-1/(1S,2R)-2, while the lowest energy structure of (R,R)-1/(1R,2S)-2 was detected after the MD and MDMM studies. The complexes with the (R,R)-1 isomer have higher total energies than those with meso-1, in accord with an NMR estimate for longer lifetimes of the complexes with meso-1.

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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 use of chiral pybox ligands imparts enantioselectivity to the Cu I-catalyzed azide-alkyne cycloaddition reaction, in the form of kinetic resolution of alpha-chiral azides and desymmetrization of gem-diazides. While levels of selectivity are modest, the results show unequivocally that the process benefits from ligand-accelerated 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

Interesting scientific research on C7H9N

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Selecting a diverse set of solvents to be included in polymorph screening assignments can be a challenging task. As an aid to decision making, a database of 218 organic solvents with 24 property descriptors was explored and visualized using multi-variate tools. The descriptors included, among others, log P, vapor pressure, hydrogen bond formation capabilities, polarity, number of pi-bonds and descriptors derived from molecular interaction field calculations (e.g., size/shape parameters and hydrophilic/ hydrophobic regions). The data matrix was initially analyzed using principal component analysis (PCA). Results from the PCA showed 57% cumulative variance being explained in the first two principal components (PCs), although relevant information was also found in the third, fourth and fifth component, revealing distinct clusters of solvents. Since five dimensions were not suitable for visual presentation, a nonlinear method, self-organizing maps (SOMs), was applied to the dataset. The constructed SOM displayed features of clusters observed in the first three PCs, however in a more compelling way. Thus, the SOM was chosen as the visually most convenient way to display the diversity of the 218 solvents. In addition, it was demonstrated how safety aspects can be considered by labeling a large fraction of the solvents in the SOM with toxicological information.

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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

What Kind of Chemistry Facts Are We Going to Learn About C7H9N

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We report a strategy for the employment of highly unstabilized anions in palladium-catalyzed asymmetric allylic alkylations (AAA). The “hard” 2-methylpyridyl nucleophiles studied are first reacted in situ with BF3?OEt2; subsequent deprotonation of the resulting complexes with LiHMDS affords “soft” anions that are competent nucleophiles in AAA reactions. The reaction is selective for the 2-position of methylpyridines and tolerates bulky aryl and alkyl substitution at the 3-, 4-, and 5-positions. Investigations into the reaction mechanism demonstrate that the configuration of the allylic stereocenter is retained, consistent with the canonical outer sphere mechanism invoked for palladium-catalyzed allylic substitution processes of stabilized anions.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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Two pentameric foldamers, Q5 and Q5C-S, containing a C?F bond were synthesized based on quinoline oligamide foldamers for the measurement of enantiomeric excess and for the determination of absolute configuration of chiral amines, diamines, amino alcohols, and alpha-amino acid esters. Chiral induction of Q5 was triggered in situ when the chiral analytes reacted with the C?F bond in Q5 by a N-nucleophilic substitution reaction, leading to a linear correlation between the CD amplitude at the region of quinoline chromophores and the ee values of the chiral analytes, which can be used for the ee determination of chiral analytes. Furthermore, the CD intensity of Q5C-S containing a chiral motif at its C-terminus enhances via remote, favorable chiral communication when the chiral induction was triggered in situ by chiral analytes at the N-terminus matches the original helicity of Q5C-S, but decreases via remote, conflicted chiral communication when the chiral induction is triggered in situ by chiral molecules at the N-terminus mismatches the original one. The system can thus be used for determination of the absolute configuration of chiral analytes, given that the chirality of the chiral motif at the C-terminus of Q5C-S is known.

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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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Dipole moments and formation equilibrium constants of a series fo pentabromophenol complexes with ternary amines in carbon tetrachloride, chloroform and 1,2-dichloroethane were measured.The values of the hydrogen bond polarity, Deltanu, were correlated with the DeltapKa parameter and the effect of the solvent activity on the charge distribution in hydrogen bonded complexes was discussed.

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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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New, highly reactive, polymerizable compounds are described, corresponding to the formula STR1 wherein R is H or lower alkyl, Z is a linking entity which is a chemical bond, lower alkylene, lower alkylenedioxy, O or the like, m is an integer 2-3 and n is 0-10. They are prepared by reaction of the corresponding 3(methylthio)phenolic compounds with the appropriate 1,4- or 1,5-alkylene bromide and converting the resulting cyclic sulfonium bromide to the zwitterion by treatment with a strong base anion-exchange resin in hydroxide form. They polymerize in a few minutes at 30-50 C. to form polymers useful as coatings.

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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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Compounds are disclosed which modulate the alpha7 nicotinic acetyl choline receptor (nAChR), having the formula (I) wherein the variables are as specified in the description and claims

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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-butyl-carboxamide, 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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The bridge-opening reaction of [(eta4-C8H 12)2Rh2(mu-Cl)2] with chiral and achiral beta-amino alcohol nucleophiles gave mononuclear complexes [(eta4-C8H12)RhCl(HN(R)?OH-kappaN)] containing the amino alcohol ligands in N-monodentate coordination; HN(R)?OH = ethanolamine (4), 2-amino-2-methyl-1-propanol (5), and either enantiomer of (R)-, (S)-2-amino-3-methyl-1-butanol (D-, L-valinol) [(R)-6, (S)-6], (R)-, (S)-2-pyrrolidinemethanol (D-, L-prolinol) [(R)-7, [S)-7], (1S,2R)-, (1R,2S)-2-amino-1-phenyl-1-propanol (D-, L-norephedrine) [(1S,2R)-8, (1R,2S)-8], and (1S.2R)-, (1R,2S)-cis-1-amino-2-indanol [(1S,2R)-9, (1R,2S)-9], Coordination of the free hydroxy function of the N,O ligands was brought about by both dehydrochlorination, which furnished the neutral valinolato chelate complex [(eta4-C8H12)Rh{(S)-H 2NCH(CHMe2)CH2O-kappaN,kappaO}], (S)-10, and by precipitation of the metal-bound chloride with TlO3SCF 3 to produce ionic chelate complexes [(eta4-C 8H12)Rh(HN(R)?OH-kappaN,kappaO}]O 3SCF3; HN(R)?OH = 2-amino-2-methyl-1-propanol (11), (S)-2-amino-3-methyl-1-butanol [(S)-12], (S)-2-pyrrolidinemethanol [(S)-13], (IR,2S)-2-amino-1-phenyl-1-propanol [(1R,2S)-14], and (1R,2S)-cis-1-amino-2- indanol [(1R,2S)-15]. Except for only two in situ characterized [{(R)-binap}Rh(H2N?OH-kappaN,kappaO)]+ cations, where H2N?OH = L-valinol or L-norephedrine, no compound containing the various N,O ligands in addition to mono- or bidentate phosphanes could be prepared. In contrast, the P2/N2-coordinated chelate complexes [{(R)-binap}Rh-(H2N?NH2)]BF 4 with H2N?NH2 = H2NCMe 2CMe2NH2 [(R)-(16)], (R,R)-H 2NCH(Ph)CH(Ph)NH2 [(R),(R,R)-17], and (R,R)-1,2-(H 2N)2C6H10 [(R),(R,R)-18] were easily obtained from [(eta4-C8H12)Rh{(R)-binap}] BF4 and 1,2-diamines. Oxidative addition of HCl to (R),(R,R)-17 produced trans-[{(R)-binap}-Rh(H)(Cl){(R,R)-H2NCH(Ph)CH(Ph)NH 2}]BF4 [(R),(R,R)-19], If activated by strong base (KOH), (R),(R,R)-17 and (R),(R,R)-19 acted as moderately active and enantioselective catalysts for the reduction of acetophenone by both direct and transfer hydrogenation: eemax: 71% (S). The crystal structures of 4, (S)-6, (R)-7, (1R,2S)-8, (S)-10, (1R,2S)-14, (1R,2S)-15, (R)-16, (R),(R,R)-17, and two alcohol/alcoholato addition compounds, [(eta4-C8H 12)Rh(H2NCMe2CH2O-kappaN,kappaO) ][(eta4-C8H12)Rh(H2-NCMe 2CH2OH-kappaN,kappaO)][(eta4-C 8H12)RhCl2] [1-2], and [(eta4- C8H12)Rh(H2NCMe2CH 2O-kappaN,kappaO)][(eta4-C8H 12)Rh(H2-NCMe2CH2OH-kappaN, kappaO)]Cl [1-3], were determined. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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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