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Design and synthesis of novel C2-symmetric chiral shift reagents derived from squaramide and their recognition of anions and chiral carboxylate anions

The novel, recyclable C2-symmetric chiral shift reagents bearing both squaramide and indanol groups have been synthesized. These squaramides were examined as chiral shift reagents, and they have a wide recognition towards chiral carboxylate anions. The squaramide derived from (1S, 2R)-1-amino-2-indanol can distinguish the absolute configuration of the guest carboxylate anion.

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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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CuI/CuBr2-catalyzed decarboxylative/A3 reaction of propiolic acids for the facile synthesis of 1,4-diheterocycle-2-butynes

A novel and efficient microwave-assisted protocol to 1,4-diheterocycle-2-butynes was successfully developed. The method is based on one-pot copper-catalyzed A3 reaction/decarboxylative coupling of a propiolic acid, a formaldehyde, and a 1,2- or 1,3-amino alcohol. This multicomponent coupling reaction provides a straight forward access to introduction oxazolidine or 1,3-oxazinane at the 1,4-position of a but-2-yne from readily available starting materials. 1,4-Diheterocycle-2-butynes with diverse substitution patterns are obtained in moderate to good 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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Reactions of Pyridine-Bases with Na/K-Alloy and Diorganylaminodifluoroboranes

Lutidines react with Na/K alloy and diorganylaminodifluoroboranes in n-hexane.The products formed depend upon the position of the methyl groups.While from 3,4-lutidine (C) the bis(lutidinyl)aminoboranes 2-5 are obtained, the 2,4-, 2,5-, and 3,5-lutidines (F, G, H) give the 11a,11b-dihydro-<1,3,2>-diazoborolo-<5,1-b;3,4-b'>-dilutidines 11-17. 4-Picoline reacts analogously to give 10.Pyridine (A) and colidine (B) give adducts with borane.From 2,3-lutidine (D), the 1,4-dihydro-1,4-bis(fluoraminoboryl)-2,3-lutidine 8 is obtained. 1H, 11B, 13C, 19F, 29Si, 15N NMR and MS data are given.For 8 and 14 the X-ray structures are reported.Key Words: Pyridine, Picoline, Lutidine, Collidine, Dilutinylaminoboranes

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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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7-AMINO-6-HETARYLIMIDAZOLO[1,2-A]PYRIMIDINE COMPOUNDS AND USE THEREOF FOR CONTROLLING HARMFUL FUNGI

The invention relates to novel 7-amino-6-hetarylimidazolo[1,2-a]pyrimidine compounds of formula (I), the salts thereof, the use of said compounds for controlling harmful fungi, and agricultural pesticides containing at least one such compound as an active component. The substituents Het, X, Y1, and Y2 in formula (I) have the following meanings: Het represents a five-membered or six-membered heteroaromatic radical which can contain one, two, three, or four heteroatoms selected among O, S, and N as ring members, said five-membered or six-membered heteroaromatic radical being optionally provided with one, two, three, or four identical or different substituents L; X represents hydrogen, OH, halogen, cyano, NR3R4, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylsulfinyl, C1-C8 alkylsulfonyl, C2-C8 alkenyl, or C2-C8 alkinyl, the seven latter radicals being optionally halogenated in full or in part and/or optionally carrying one, two, or three substituents selected among nitro, cyano, C1-C2 alkoxy, C1-C4 alkoxycarbonyl, amino, C1-C4 alkylamino, and di-C1-C4 alkylamino. R3 and R4 independently have the meanings indicated for R1 or R2; Y1, Y2 independently represent hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkyl halide, C3-C7 cycloalkyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C1-C4 haloalkoxy; and R1, R2 have the meanings indicated in the claims and the description.

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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

Properties and Exciting Facts About (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Enantioselective alpha-hydroxylation of -ketoamides

The first enantioselective alpha-hydroxylation reaction of alpha-substituted -ketoamides has been developed by using the commercially available hydroquinine/TBHP system. The tertiary alcohols are obtained in good to high yield and up to 83% ee, which can be improved by a single crystallization.

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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

Extracurricular laboratory:new discovery of 2,4-Dimethylpyridine

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Bimetallic C-C Bond-Forming Reductive Elimination from Nickel

Ni-catalyzed cross-coupling reactions have found important applications in organic synthesis. The fundamental characterization of the key steps in cross-coupling reactions, including C-C bond-forming reductive elimination, represents a significant challenge. Bimolecular pathways were invoked in early proposals, but the experimental evidence was limited. We present the preparation of well-defined (pyridine-pyrrolyl)Ni monomethyl and monophenyl complexes that allow the direct observation of bimolecular reductive elimination to generate ethane and biphenyl, respectively. The sp3-sp3 and sp2-sp2 couplings proceed via two distinct pathways. Oxidants promote the fast formation of Ni(III) from (pyridine-pyrrolyl)Ni-methyl, which dimerizes to afford a bimetallic Ni(III) intermediate. Our data are most consistent with the subsequent methyl coupling from the bimetallic Ni(III) to generate ethane as the rate-determining step. In contrast, the formation of biphenyl is facilitated by the coordination of a bidentate donor ligand.

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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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REGIOINTEGRITY OF CARBANIONS DERIVED BY SELECTIVE METALATIONS OF DIMETHYLPYRIDINES AND -QUINOLINES

Metalation of 2,4-dimethylpyridine and -quinolines by strong basic reagents in ethyl ether in the absence of HMPA affords 2-lithiomethyl derivatives regardless of the reaction length.The use of THF in such metalations promotes the formation of the 2-lithiomethyl reagents which isomerize to the more thermodynamically stable 4-lithiomethyl derivatives after relatively long reaction periods or in the presence of amines or an excess of the parent heterocycle.The latter derivatives appear to be formed directly from the heterocycles in ammonia or in the presence of HMPA.The results are discussed in terms of “coordination-only” versus “acid-base” limiting mechanisms for metalations as a function of ion pairing.NMR spectra for certain of the carbanions in ethyl ether and THF are described which support the above concepts.Related metalations of 2,4-dimethylquinoline-N-oxide give only the 2-lithiomethyl derivative.Similar reactions of 7-hydroxy-2,4-dimethyl-1,8-naphthyridine lead in synthetically useful yields to derivatization of the 2- and 4-methyl groups via dianions by using n-butyllithium in ethyl ether and sodium amide in liquid ammonia, respectively, followed by the addition of appropriate electrophiles.

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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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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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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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One of the major reasons for studying chemical kinetics is to use measurements of the macroscopic properties of a system, COA of Formula: C9H11NO, such as the rate of change in the concentration of reactants or products with time.In a article, mentioned the application of 126456-43-7, Name is (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol, molecular formula is C9H11NO

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