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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

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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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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

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Low nanomolar corticotropin releasing factor type-1 (CRF1) receptor antagonists containing unique indanylamines were identified from the heteroatom-linked pyrazine chemotype. The most potent indanylpyrazine had a Ki = 11 ± 1 nM. The oxygen-linked pyrazinyl derivatives were prepared through a copper-catalyzed coupling of a pyridinone to a bromo- or iodopyrazine.

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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 compounds are of the class of benzisoxazolyl-, pyridoisoxazolyl-and benzthienyl-phenoxy derivatives, useful as D4 antagonists. Said compounds are useful for the treatment of medical conditions mediated by inhibition of D4 receptor. These conditions comprise, for example, Attention Deficit Hyperactivity Disorder, Obsessive-Compulsive Disorder, Psychoses, Substance Abuse, Substance Dependence, Parkinson’s Disease, Parkinsonism, Tardive Diskinesia, Gilles de la Tourette Syndrome, Conduct Disorder, and Oppositional Defiant Disorder. A further aspect of the invention is to provide a pharmaceutical composition, intermediates, and a method of making said class of compounds.

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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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Transposition of the pyridyl nitrogen from the P3 substituent to the P1? substituent in HIV-1 protease inhibitors (PI) affords compounds such as 3 with an improved inhibitory profile against multiple P450 isoforms. These compounds also displayed increased potency, with 3 inhibiting viral spread (CIC95) at <8 nM for every strain of PI-resistant HIV-1 tested. The poor to modest bioavailability of these compounds may correlate in part to their aqueous solubility. The design and synthesis of related molecules that are more effective, more selective, and less toxic than aspirin are important objectives of biomedical research.category: chiral-nitrogen-ligands, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 126456-43-7, in my other articles.

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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By tethering of a polar hydrophilic group to the P1 or P1′ substituent of a Phe-based hydroxyethylene isostere, the antiviral potency of a series of HIV protease inhibitors was improved. The optimum enhancement of anti-HIV activity was observed with the 4-morpholinylethoxy substituent. The substituent effect is consistent with a model derived from inhibitor docked in the crystal structure of the native enzyme. An X-ray crystal structure of the inhibited enzyme determined to 2.25 A verifies the modeling predictions.

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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 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