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Dynamic Kinetic Resolution of Heterobiaryl Ketones by Zinc-Catalyzed Asymmetric Hydrosilylation

A diastereo- and highly enantioselective dynamic kinetic resolution (DKR) of configurationally labile heterobiaryl ketones is described. The DKR proceeds by zinc-catalyzed hydrosilylation of the carbonyl group, thus leading to secondary alcohols bearing axial and central chirality. The strategy relies on the labilization of the stereogenic axis that takes place thanks to a Lewis acid?base interaction between a nitrogen atom in the heterocycle and the ketone carbonyl group. The synthetic utility of the methodology is demonstrated through stereospecific transformations into either N,N-ligands or appealing axially chiral, bifunctional thiourea organocatalysts.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Asymmetrische Katalysen. XLVI. Enantioselektive Hydrosilylierung von Ketonen mit 2 und optisch aktiven Stickstoff-Liganden

The synthesis and characterisation of 16 optically active nitrogen ligands, namely, pyridinethiazolidones, pyridinethiazolines, pyridinimidazolines, Schiff bases and bipyridines, are described.These ligands are used as cocatalysts together with the procatalyst 2 in the catalytic hydrosilylation of prochiral ketones with diphenylsilane.With these homogeneous in situ catalysts, optically active 1-phenylethanol is produced from acetophenone after hydrolysis of the silyl ether.The diastereomers of N-(1-phenylethyl)-2-(2-pyridinyl)-thiazolidine-4-one give opposite optical inductions.The best optical purity of 71.6percent ee is obtained with a pinanyl-substituted bipyridine.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 29841-69-8, molcular formula is C14H16N2, introducing its new discovery. Recommanded Product: (1S,2S)-(-)-1,2-Diphenylethylenediamine

Correction: Polyfunctional Imidazolium Aryloxide Betaine/Lewis Acid Catalysts as Tools for the Asymmetric Synthesis of Disfavored Diastereomers (Journal of the American Chemical Society (2019) 141 (12029?12043) DOI: 10.1021/jacs.9b04902)

Page 12035 and Supporting Information pp S91?S94. It has come to our attention that the wrong initial concentration of 1a was erroneously used in two experiments of the ?same excess? protocol.1 The experiments were thus repeated (0.055 rather than 0.06 mol/L of 1a was erroneously used before), and an excellent overlay of the ?time-adjusted same excess? reaction profiles and the standard reaction profile, as previously presented, was found. This indicates that no significant catalyst deactivation takes place and that the active catalyst concentration remains constant during the catalytic reaction. The conclusions are thus not affected by the unintentional error. The corrected Figure 1 is shown below, and a corrected.(Figure Presented) Supporting Information file is available, in which pp S91?S94 have been replaced, in which the correct kinetic experiments are described, including raw data. We apologize for any inconvenience.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 29841-69-8, name is (1S,2S)-(-)-1,2-Diphenylethylenediamine, introducing its new discovery. Safety of (1S,2S)-(-)-1,2-Diphenylethylenediamine

All-carbon quaternary stereogenic centers by enantioselective Cu-catalyzed conjugate additions promoted by a chiral N-heterocyclic carbene

(Chemical Equation Presented) Necessity is the mother of invention: When the available catalysts do not cut it, a new one has to be developed. A chiral N-heterocyclic carbene (NHC) is used in the first catalytic asymmetric conjugate addition of alkyl- and arylzinc reagents to gamma-keto esters (see scheme).

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Chiral phosphoramide-catalyzed aldol additions of ketone trichlorosilyl enolates. Mechanistic aspects

The mechanism of the catalytic, enantioselective addition of trichlorosilyl enolates to aldehydes has been investigated. Kinetic studies using ReactIR and rapid injection NMR (RINMR) spectroscopy have confirmed the simultaneous operation of dual mechanistic pathways involving either one or two phosphoramides bound to a siliconium ion organizational center. This mechanistic dichotomy was initially postulated on the basis of catalyst loading studies and nonlinear effects studies. This duality explains the difference in reactivity and stereoselectivity of various classes of phosphoramides. Determination of Arrhenius activation parameters revealed that aldol addition occurs through the reversible albeit unfavorable formation of an activated complex, and natural-abundance 13C NMR kinetic isotope effect (KIE) studies have determined that the turnover limiting step is the aldol addition. A thorough examination of a range of phosphoramides has established empirical structure-activity selectivity relationships. In addition, the effects of catalyst loading, rate of addition, solvents, and additives have been studied and together allow the formulation of a unified mechanistic picture for the aldol addition.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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CHIRALITY SENSING WITH MOLECULAR CLICK CHEMISTRY PROBES

The present invention relates to an analytical method that includes providing a sample potentially containing a chiral analyte that can exist in stereoisomeric forms, and providing a probe selected from the group consisting of coumarin-derived Michael acceptors, dinitrofluoroarenes and analogs thereof, arylsulfonyl chlorides and analogs thereof, arylchlorophosphines and analogs thereof, aryl halophosphites, and halodiazaphosphites. The sample is contacted with the probe under conditions to permit covalent binding of the probe to the analyte, if present in the sample; and, based on any binding that occurs, the absolute configuration of the analyte in the sample, and/or the concentration of the analyte in the sample, and/or the enantiomeric composition of the analyte in the sample is/are determined. The probe may be a coumarin-derived Michael acceptor, a di nitrofluoroarene or analog thereof, an arylsulfonyl chloride or analog thereof, an arylchlorophosphine or analog thereof, an aryl halophosphite, or a halodiazaphosphite.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Dielectric anisotropy of a homochiral rare-earth metal complex

A homochiral rare-earth metal Tb complex that exhibited a very large dielectric anisotropic property with a temperature-independent feature is obtained. Our findings on high-dielectric anisotropy will provide a new impetus in this field of materials science. The Royal Society of Chemistry.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Chiral diphenylselenophosphoramides: A new class of chiral ligands for the titanium(IV) alkoxide-promoted addition of diethylzinc to aldehydes

Chiral C2-symmetric diphenylselenophosphoramides 1 and 2 were prepared from the reaction of diphenylselenophosphinic chloride with (1R,2R)-(-)-1,2-diaminocyclohexane and (1R,2R)-(+)-1,2-diphenylethylenediamine, respectively, in high yields. Another novel chiral ligand 3 was prepared from the reaction of diphenylselenophosphinic chloride with (R)-(+)-1,1′-binaphthyl-2,2′-diamine using butyllithium as the base. The ligands were used as catalytic chiral ligands in the titanium(IV) alkoxide-promoted enantioselective addition reaction of diethylzinc to aldehydes. Copyright (C) 2000 Elsevier Science Ltd.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Diastereoselective Cycloaddition of N-Lithiated Azomethine Ylides to (E)-alpha,beta-Unsaturated Esters Bearing a C2-Symmetric Imidazolidine Chiral Controller

The 1,3-dipolar cycloaddition of N-metalated ylides to chiral (E)-3-(1,3-disubstituted 4,5-diphenylimidazolidin-2-yl)propenoates proceeded highly diastereoselectively.The previously unknown absolute configuration of optically pure 1,2-dianilino-1,2-diphenylethane was determined from the absolute configuration of the cycloadducts.What diastereotopic olefin face of the alpha,beta-unsaturated ester was attacked by the ylide was found to depend dramatically upon the nature of N substituents of the chiral controller as well as upon the bulkiness of the ester moiety of the ylide.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A pH-Responsive Soluble-Polymer-Based Homogeneous Ruthenium Catalyst for Highly Efficient Asymmetric Transfer Hydrogenation (ATH)

A pH-responsive polymer has been synthesized successfully by means of copolymerization of dimethyl aminopropyl acrylamide (DMAPA) and N-p-styrenesulfonyl-1,2-diphenylethylenediamine (V-TsDPEN). The pH-responsive polymer coordination ruthenium complex was thus prepared and employed as an efficient catalyst for the asymmetric transfer hydrogenation (ATH) of various ketones. The polymer catalyst exhibited an attractive pH-induced phase-separable behavior in water: it could be dissolved in water when the pH of the solution was lower than 6.5 at the beginning of the reaction, but was precipitated completely from water when the pH of the solution was above 8.5 after reaction. Additionally, the catalysts were highly efficient for the ATH of a wide range of substrates that bore different functional groups and could be recycled easily from the aqueous solution by means of self-separation. They could be recycled eight times without significant changes in catalytic activity and enantioselectivity.

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Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI