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A series of methylated and octylated pyridinium and quinolinium containing thiourea salts with a chiral 2-indanol substituent are reported. These organocatalysts are positively charged analogues of privileged bis(3,5-trifluoromethyl)phenyl substituted thioureas, and are found to be much more active catalysts despite the absence of an additional hydrogen bond donor or acceptor site (i.e., the presence of a heteroatom-hydrogen or heteroatom). Friedel-Crafts reactions of trans-beta-nitorostyrenes with indoles are examined, and good yields and enantioselectivities are obtained. Mechanistic studies indicate that this is a second-order transformation under the employed conditions, and is consistent with the dimer of the thiourea being the active catalyst. Charged organocatalysts, consequently, represent an attractive design strategy for catalyst development.

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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 dimeric amino alcohol derived Schiff bases with various chiral amino alcohols and their corresponding bimetallic titanium complex were generated in situ. Thereafter with the in situ generated complexes, the asymmetric oxidation of prochiral aryl alkyl sulfides has been investigated using aqueous H2O2 as a terminal oxidant. During the study we found that the use of methanol or tert-butanol as an additive improved the catalytic activity in terms of both conversion and enantioselectivity. Moreover we observed a co-operative effect of the two reactive units of the bimetallic complex, which results in high reactivity as well as enantioselectivity compared to the corresponding monomeric complex. With this improved catalytic system several aryl alkyl sulfides and 1,3-dithianes were oxidised to the corresponding sulfoxides with good to high enantioselectivity (ee 78-99%) and conversion (70-99%). Unlike the monomer, oxidation of substrates like benzyl phenyl sulfide was achieved with high enantioselectivity as well as high yield.

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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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Formula: C9H11NO, Chemo-enzymatic cascade processes are invaluable due to their ability to rapidly construct high-value products from available feedstock chemicals in a one-pot relay manner. 126456-43-7, Name is (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol,introducing its new discovery.

Binuclear Ni(II) chelating complex with chiral Schiff base 1-((E)-(((1S,2R)-2-hydroxy-2,3-dihydro-1H-inden-1-yl)imino)methyl)naphthalene-2-ol [Ni2L2] has been synthesized. The structure of [Ni2L2] was elucidated with single-crystal X-ray diffraction, spectroscopic (UV?vis, FTIR, mass) analysis and substantiated with computational (DFT) method. The crystal system of binuclear complex is monoclinic with space group P21/c. The asymmetric unit having two tridentate OON-donor sets are in slightly distorted square-planar geometry around each Ni(II) center. The distortion is due to strong coordination between two Ni(II) ions. The stabilization of complex [Ni2L2] occurs due to noncovalent interactions and hydrogen bonding (C?H?C and C?H?O), H?H, O?H, C?H, and C?H?pi stacking interactions, and van der Waals interactions. DFT optimization, with little acceptable discrepancies, correlate with the X-ray diffraction data as well as TD DFT optimization for electronic transitions of the complex showing acceptable alignment with spectroscopic data. The complex displays appreciable inclination towards DNA-binding with calf-thymus DNA (CT DNA) and the DNA-binding studies were carried out by UV?visible spectroscopy, fluorescence spectroscopy, cyclic voltammetry, viscosity measurements, and CD spectroscopy. The DNA-binding study reveals that the order of binding constant value is in 105 M? 1, supporting the effective efficiency of binding and the modes of binding are intercalation and groove.

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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 process for making a clinically efficacious HIV protease inhibitor eliminates one step in its synthesis, by an alternative convergent synthesis using 2(S)-4-picolyl-2-piperazine-t-butylcarboxamide as an intermediate.

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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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Disclosed herein are methods of forming chiral 1,2-aminoalcohols and alpha-aminoacids from alkene starting materials by way of an enzymatic cascade reaction sequence that may be accomplished in a single reaction vessel without the need to isolate any intermediates. Also disclosed herein are recombinant nucleic acids, vectors and host cells for use in the methods of the invention.

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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 optically active proton-ionizable lariat crown ether derivative 2 was prepared. Host 2 displays enantiomeric selectivity toward phenylglycinol (Klarge/Ksmall=3.2) and phenylalaninol (Klarge/Ksmall=1.7). The key intermediate 1 was synthesized in two steps from commercially available binaphthol in 30% yield.

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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 addition: A copper/N-heterocyclic carbene(NHC)-catalyzed 1,4-addition of organoboronates to alkylidene cyanoacetates was developed, in which the catalytic cycle is proposed to consist of a transmetalation/insertion/ligand exchange. An effective asymmetric variant has also been achieved by the use of a chiral NHC ligand (see scheme). 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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A readily available bisoxazolidine ligand was found to catalyze the asymmetric alkylation of aldehydes with Et2Zn and less reactive Me2Zn, providing high yields and ee’s in both reactions. The bisoxazolidine-catalyzed alkylations and alkynylation of benzaldehyde show a positive nonlinear effect that cannot be accounted for by Kagan’s MLn model. The chiral amplification originates from selective phase distribution favoring enrichment of the major enantiomer of the scalemic catalyst in solution.

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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 enantioselective construction of carbon?heteroatom and carbon?carbon bonds that are alpha to ketones leads to the formation of substructures that are ubiquitous in natural products, pharmaceuticals and agrochemicals. Traditional methods to form such bonds have relied on combining ketone enolates with electrophiles. Reactions with heteroatom-based electrophiles require special reagents in which the heteroatom, which is typically nucleophilic, has been rendered electrophilic by changes to the oxidation state. The resulting products usually require post-synthetic transformations to unveil the functional group in the final desired products. Moreover, different catalytic systems are typically required for the reaction of different electrophiles. Here, we report a strategy for the formal enantioselective alpha-functionalization of ketones to form products containing a diverse array of substituents at the alpha position with a single catalyst. This strategy involves an unusual reversal of the role of the nucleophile and electrophile to form C?N, C?O, C?S and C?C bonds from a series of masked ketone electrophiles and a wide range of conventional heteroatom and carbon nucleophiles catalysed by a metallacyclic iridium catalyst.

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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 of the enantiomers of alpha,alpha?- bis(trifluoromethyl)-1,8-anthracenedimethanol is described, and their conformational behaviour studied. These enantiomers are very active when used as chiral solvating agents in the presence of several 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