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The bidentate complexes of (R,R)- and meso-alpha,alpha?- bis(trifluoromethyl)-9,10-anthracenedimethanol with cis-1-amino-2-indanol

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£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Catalytic enantioselective Steglich rearrangements using chiral N-heterocyclic carbenes

The evaluation of a range of enantiomerically pure NHCs, prepared in situ from imidazolinium or triazolium salt precatalysts, to promote the catalytic enantioselective Steglich rearrangement of oxazolyl carbonates to their C-carboxyazlactones, is reported. Modest levels of enantioselectivity (up to 66% ee) are observed using oxazolidinone derived NHCs.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Lewis acid-catalyzed asymmetric diels-alder reactions using chiral sulfoxide ligands: chiral 2-(arylsulfinylmethyl)-1,3-oxazoline derivatives.

New chiral sulfoxide-1,3-oxazoline ligands have been developed as chiral ligands for Lewis acid-catalyzed asymmetric Diels-Alder reactions. The use of chiral sulfinyl 1,3-oxazoline ligands in copper(II)-catalyzed asymmetric Diels-Alder reactions provided an endo cycloadduct as a major product with moderate enantioselectivity. A rationale is proposed for the mechanism of the asymmetric induction.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Structure-based design, synthesis, and biological evaluation of irreversible human rhinovirus 3C protease inhibitors. 3. Structure-activity studies of ketomethylene-containing peptidomimetics

The structure-based design, chemical synthesis, and biological evaluation of various ketomethylene-containing human rhinovirus (HRV) 3C protease (3CP) inhibitors are described. These compounds are comprised of a peptidomimetic binding determinant and an ethyl propenoate Michael acceptor moiety which forms an irreversible covalent adduct with the active site cysteine residue of the 3C enzyme. The ketomethylene-containing inhibitors typically display slightly reduced 3CP inhibition activity relative to the corresponding peptide-derived molecules, but they also exhibit significantly improved antiviral properties. Optimization of the ketomethylene-containing compounds is shown to provide several highly active 3C protease inhibitors which function as potent antirhinoviral agents (EC90 = < 1 muM) against multiple virus serotypes in cell culture. Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. Computed Properties of C9H11NO, 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£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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A discovery tool at work: The unexpected properties of a two-carbon residue

We report the very easy preparation of novel peptides 6a-n as represented by CF3CH2(L)Phe(L)IleOtBu (6a), a prospective antitumor compound. Peptides such as 6a are directly obtained via standard chemistry from a novel class of amino acids, Nalpha-trifluoroethyl amino acids 4. In fact, unexpectedly, the Nalpha-1,1,1-trifluoroethyl substitution completely deactivates the alpha-nitrogen. That is, compounds 4 behave exactly like Nalpha-protected amino acids, and take part in standard peptide synthesis accordingly. Representative compounds 4a-c are prepared by reaction of commercial amino acid t-butyl esters 2a-c with 1 eq iodonium salt 1 in dichloromethane/water at 22C in 1 h or less. The reaction is promoted by NaHCO3 (1.5 eq). The intermediate Nalpha-1,1,1-trifluoroethyl t-butyl esters 3a-c are hydrolyzed and separated from coproducts at the same time by treatment with aqueous HCl at 22C. Evaporation of the acid extracts provides analytically pure 4a-c in 78-98% yields.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Development of column-free alkoxycarbonyl, aryloxycarbonyl, and acyl transfer reagents

Easy-to-handle alkoxycarbonyl, aryloxycarbonyl, and acyl transfer reagents, which contain 3-nitro-1,2,4-triazole (NT) as a leaving group, were developed. With these reagents (NT reagents), which are stable nonhygroscopic crystalline materials, the reactions can be accomplished in about 5 min, and product can be isolated without tedious column chromatographic purification.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Synergistic Stereocontrol in the Enantioselective Ruthenium-Catalyzed Sulfoxidation of Spirodithiolane-Indolones

A chiral ruthenium catalyst was developed for the enantioselective sulfoxidation of the title compounds. The catalyst combines two elements of chirality, a chiral pybox ligand and a chiral bicylic lactam unit, to which the ligand is attached. The latter unit was shown to improve significantly the performance of the catalyst by exposing one of the two enantiotopic sulfur atoms to the active site via hydrogen-bond mediated coordination. Ten differently substituted substrates were converted into the respective sulfoxides in yields of 52-71% and with ?90% ee. Hand-in-hand: Two spatially remote chiral entities act synergistically together in the Ru-catalyzed sulfoxidation reaction of the title compounds. Hydrogen bonds and pi-pi interactions are invoked to explain the preferential formation of a single stereoisomer in this reaction. High enantioselectivities (90-99% ee).

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Quantitative Chiroptical Sensing of Free Amino acids, Biothiols, Amines and Amino Alcohols with an Aryl Fluoride Probe

The comprehensive determination of the absolute configuration, enantiomeric ratio and total amount of standard amino acids by optical methods adaptable to high-throughput screening with modern plate readers has remained a major challenge to date. We now present a small molecular probe that smoothly reacts with amino acids and biothiols in aqueous solution and thereby generates distinct chiroptical responses to accomplish this task. The achiral sensor is readily available, inexpensive and suitable for chiroptical analysis of each of the 19 standard amino acids, biothiols, aliphatic and aromatic amines and amino alcohols. The sensing method is operationally simple and data collection and processing are straightforward. The utility and practicality of the assay are demonstrated with the accurate analysis of ten aspartic acid samples covering a wide concentration range and largely varying enantiomeric compositions. Accurate er sensing of 85 scalemic samples of Pro, Met, Cys, Ala, methylpyrrolidine, 1-(2-naphthyl)amine and mixtures thereof is also presented.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Chiroptical Asymmetric Reaction Screening via Multicomponent Self-Assembly

Self-assembly of a stereodynamic phosphine ligand, Pd(II), and a chiral amine, amino alcohol, or amino acid generates characteristic UV and CD signals that can be used for quantitative stereochemical analysis of the bound substrate. A robust mix-and-measure chiroptical sensing protocol has been developed and used to determine the absolute configuration, ee, and yield of an amine produced by Ir-catalyzed asymmetric hydrogenation of an iminium salt. The analysis requires only 1 mg of the crude reaction mixture and minimizes cost, labor, time, and waste.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Regioselective synthesis of 1,4-disubstituted imidazoles

A short and efficient synthesis of 1,4-disubstituted imidazoles has been developed which provides the desired products with complete regioselectivity. This protocol allows preparation of compounds which are challenging to prepare by current literature methods in a regioselective fashion, a sterically and electronically diverse range of N-substituents being accessible. The sequence involves an unusual double aminomethylenation of a glycine derivative, to yield a 2-azabuta-1,3-diene, onto which addition of an amine nucleophile results in a transamination/cyclization to prepare the substituted imidazole. The cyclization event is surprisingly insensitive to steric and electronic variations on the amine component, enabling a diverse range of imidazoles to be prepared.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis