Our Top Choice Compound: 2,4-Dimethylpyridine

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A new aerobic copper-catalyzed three-component synthesis of azaaryl-substituted quinazolines has been developed, which featured inexpensive methylazaarenes as C1 sources, easily available copper salts as the catalysts and O2 as a sole oxidant. The transformation had very good substrate applicability towards methylazaarenes, and various azaaryl-substituted quinazolines were obtained in moderate to good yields.

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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 phosphinite derivative that can be easily prepared in two steps from commercially available aminoindanol was found to be an effective catalyst for enantioselective acylation of diols. For the asymmetric desymmetrization of meso-1,2-diols, the corresponding monoester was obtained in up to 95% ee from the reaction in the presence of 5 mol % 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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Acid-base equilibria of 3-hydroxy-2,4,6-trinitropyridine with selected pyridine bases have been studied in aqueous solution.Spectrophotometric stability constants have been determined together with enthalpies and entropies of formation.The nature of the intermolecular interactions was confirmed by quantum chemical calculations.

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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

Our Top Choice Compound: (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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The importance of chiral organic intermediates in various industrial sectors cannot be underestimated. Lipases and their use in combination with metal catalysts is a promising and facile approach to obtain enantiomerically pure chiral intermediates like alcohols and amines. The area of lipase-mediated kinetic resolution (KR) and its dynamic counterpart (dynamic kinetic resolution, DKR) employing lipases and metal based racemization catalysts has shown extensive and stimulating advances in the recent years. The present review highlights the recent progress in this field pertaining to the development of transition metal based racemization catalysts for utilization in DKR protocols and also widening of the application for a range of chiral alcohols and amines that are employed as substrates in lipase catalyzed KR. In addition, the developments in the lipase catalyzed protocols to access other chiral intermediates such as esters, amides, aminoacids etc and their derivatives are also 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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A continuous micro-structured reactor equipped with a perforated (5 mum) membrane is used for the investigation of the gas-liquid-solid asymmetric hydrogenation of ethylpyruvate on a Pt/gamma-Al2O3 catalyst modified with chiral inductors under high hydrogen pressure (45 bar). Up to eight chiral inductors have been evaluated, the best enantioselectivity (63%) being obtained with cinchonidine. The very low reaction volume (100 mul) offers short operating time. Solvent effect, deactivation studies and the effect of modifier leaching are also reported.

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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 scope and relative rates of intramolecular cycloaddition reactions of methyl-substituted 2-(3-butenyl)-1,2-dihydropyridines 4 have been studied.Cycloadducts 5 can be rearranged to 14 upon reaction with bromine, except when olefinic methyl groups are present.

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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

Extracurricular laboratory:new discovery of (+)-Sparteine

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The synthetic strategies towards tetraphenylene derivatives are comprehensively summarized in this review. Recent advances in the functionalized tetraphenylene skeleton for research into their structurally unique properties are described together with their potential applications.

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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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2,6-lutidine is formed from acetone, methanol and ammonia over ZSM-5 type zeolitic catalysts. Selectivity to 2,6-lutidine is found to be highest at relatively high Si/Al ratios. At higher Si/Al ratios a lower steady state adsorption of lutidine (0.6 lutidine/Al) is observed under reaction conditions. Possible mechanisms are discussed in the light of an experiment with 13C-labelled methanol.

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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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Figure Presented. Addition of organocuprates, generated in situ using an excess of a 1:2 mixture of CuIDMS and Grignard reagent, to N-enoyl oxazolidinethiones in the presence of excess TMSI gave preferentially the anti diastereomer where the addition took place when the conformation of the substrate was syn-s-cis. The reaction was investigated with indene-based and three different phenyl glycine derived oxazolidinethiones.

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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 effect of the structure of tertiary amines on the rate of forming vinylammonium salts has been studied.These salts are intermediates in the nucleophilic catalysis of SNVin-substitution.The example used is the aminolysis of p-nitrophenyl trans-beta-chlorovinyl sulfone in acetonitrile at 25 deg C.It was discovered that these reactions possess a higher sensitivity towards the effect of the electronic and spatial factors of the amine structure than does the vinylation of nucleophiles, primary and secondary amines, by the salts indicated.It was shown by analyzing the results that the process may be proceeding in different situations (accumulation or rapid consumption of the intermediate) depending on the nature of the catalyst and nucleophile.Various types of catalysis are therefore being effected, such as general-base, nucleophilic, and nucleophilic with general base assistance.

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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