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Molecular structures of Ugi’s amine ferrocene-conjugates with R,R-tartaric acid and DFT calculations versus experimental resolution of their diastereomers

Classical synthetic approach to highly enantiomeric-enriched ferrocenes relies on the formation of their conjugates with (R,R)-tartaric acid. Herein, the quantum chemical calculations based on X-ray data as an initial approximation, were carried out for both (R)- and (S)-diastereomers of N,N-(dimethyl-1-ferrocenyl)ethylamine (Ugi’s amine) with (R,R)-tartaric acid. A high correlation between the experimental data and the calculated Gibbs free energies values of solvation was obtained. Based on the advanced DFT calculations, the chemical aspects of the separation of the diastereomeric complexes of (R)- and (S)-FcCH(CH3)N(CH3)2 with (R,R)-tartaric acid were clarified. Quantum chemical calculations made it possible to justify the use of methanol as a solvent in the successful separation of the diastereomeric complexes of the Ugi’s amine. This mathematical approach can be used in practice to separate racemates of other bioactive ferrocene compounds, for example, ferrocenyl alkyl azoles.

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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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Optically Active Transition-Metal Complexes. 9.1 A General Stereoselective Route to alpha-Chiral (A)-Tricarbonyl(eta6-ethylbenzene)chromium Complexes. Novel Organometallic Phosphine Catalysts for the Asymmetric Hydrovinylation Reaction

Treatment of (R)-[{alpha-(dimethylamino)ethyl}-eta6-benzene]Cr(CO)3 with esters of chloroformic acid leads to stereoselective substitution of the dimethylamino group for a chloro substituent. The reaction can be extended to systems in which the chromium arene complex, after metalation, is diastereoselectively substituted in the ortho position with carbon and silicon electrophiles to generate planar chirality. The chloro group in turn can be replaced stereoselectively for various phosphorus, nitrogen, and oxygen nucleophiles. Both substitution reactions in the benzylic position proceed via retention of configuration. The addition of cyanide is not stereospecific. The phosphine derivatives are efficient catalysts for the enantioselective hydrovinylation of styrene to 3-phenyl-1-butene. X-ray crystal structures establish the absolute configuration of (R)-[(alpha-chloroethyl)eta6-benzene]Cr(CO)3, (R)-[{alpha-(diphenylphosphanyl)ethyl}-alpha6-benzene]Cr(CO) 3, and (pS,S)-[l-(alpha-cyanoethyl)-2-methyl-eta6-benzene]Cr(CO) 3.

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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

Brief introduction of 31886-57-4

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. Computed Properties of C14H19FeN, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 31886-57-4, in my other articles.

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Insight into the Thermal Ring-Opening Polymerization of Phospha[1]ferrocenophanes

A mixture of cis/trans isomers of phospha[1]ferrocenophanes equipped with one iPr group at the alpha position to the bridging PhP moiety was prepared. Both isomers (cis-4 and trans-4) were obtained as racemates and could be separated so that their thermal properties were investigated individually. The molecular structure of cis-4 was determined by single-crystal X-ray analysis showing a tilt angle alpha=26.35(8). Interconversion between both isomers occurred in the melt at elevated temperatures and revealed that the trans isomer is thermodynamically more stable. Structural and thermodynamic data was complemented by DFT calculations (B3PW91/6-311+G(d,p) and B3PW91-D3(BJ)/6-311+G(d,p)). Performance of thermal ring-opening polymerization (ROP) of trans-4 at 230 C gave polymers and cyclic oligomers. Gel permeation chromatography (GPC) of the sulfurized polymer resulted in a molecular weight of 62.5 kDa (Mw) and a polydispersity index of 1.39 (PDI). Mass spectrometric analysis of the oligomers showed the presence of cyclic species from dimers to heptamers. After sulfurization, preparative thin layer chromatography led to the separation of three isomeric dimers. Structural characterization of these dimers by single-crystal X-ray analysis led to the conclusion that the Fe?Cp bond breaks during the thermal ROP process. A mechanism similar to the known mechanism of the photolytic ROP of ferrocenophanes is proposed.

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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

Final Thoughts on Chemistry for (S)-N,N-Dimethyl-1-ferrocenylethylamine

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Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality

Reaction of [IrCp?Cl2]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6H4) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp?,RIr?. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc,Sp,RIr. Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.

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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

Discovery of (S)-N,N-Dimethyl-1-ferrocenylethylamine

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PROCESS FOR THE SYNTHESIS OF ARYL HYDRAZINES

The invention relates to a process for the synthesis of aryl hydrazinesof formula I or a salt thereof, which process comprises subjecting an arene of formula II to a coupling reaction with hydrazine or a derivative thereof, wherein the coupling reaction is conducted in the presence of a catalyst comprising palladium and a diphosphine ligand, wherein the phosphorus atoms are connected through two, three, four, or five atoms selected from car- bon, nitrogen, oxygen or iron, and in which the non-connecting phosphorus substituents are C1- C 10-alkyl or C3-C10-cycloalkyl, wherein the amount of Pd used is up to 0.5 mol-% relative to the amount of arene of formula II; and a base.

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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

Extended knowledge of (S)-N,N-Dimethyl-1-ferrocenylethylamine

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Synthesis and electrochemical properties of mono- And (¡À)-l,2-dia!kylferrocenes and alkylferrocenium hexafluorophosphates in aqueous and micellar media

Simple methods have been developed for the preparation of a series of n-alkylferrocenes H(CH2)Fc (n = 3, 5-8, or 12) based on Friedel-Crafts acylation of ferrocenes followed by reduction of the corresponding ketones with Zn amalgam. The properties of H(CH2>nFc and the corresponding ferrocenium ions in micellar aqueous solutions and the behavior of watersoluble cations H(CH2)nFc+ in the absence of micelles were studied by cyclic voltammetry. In all cases, the formal redox potentials of ferrocenes (? ‘) increase linearly as n increases up to 8. Whether micelles are present or not, the corresponding correlation equation has the following form: ?”‘= a + pn, where beta= 29 mV in all cases. The synthesis of (¡À)-l-ethyI-2methylferrocene from racemic a-dimethylaminoethylferrocene is reported.

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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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Electric-Field-Enhanced Adsorption of Chiral Molecules on Ferromagnetic Substrates

The effect of an electric field on the adsorption of oligopeptides and DNA on a ferromagnetic substrate magnetized perpendicular to the surface was investigated. The direction of the magnetic moment of the substrate defines different adsorption rates for different enantiomers, and the direction of the electric field, perpendicular to the surface, defines different adsorption rates depending on the direction of the dipole moment of the adsorbed molecules.

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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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Stereoselective and Stereospecific Reactions of Cobalt Sandwich Complexes: Synthesis of a New Class of Single Enantiomer Bulky Planar Chiral P?N and P?P Ligands

Starting from (eta5-acetylcyclopentadienyl)(eta4-tetraphenylcyclobutadiene)cobalt(I), highly enantioselective (99 % ee) (S)-CBS catalysed ketone reduction followed by stereospecific alcohol-azide exchange, azide reduction and dimethyllation gave (R)-(eta5-alpha-N,N-dimethylaminoethylcyclopentadienyl)(eta4-tetraphenylcyclobutadiene) cobalt(I) (Arthurs? amine). This underwent highly diastereoselective cyclopalladation to give di-mu-acetate-bis-(R)-[(eta5-(Sp)-2-(alpha-N,N-dimethylaminoethyl)cyclopentadienyl, 1-C, N)(eta4-tetraphenylcyclobutadiene)cobalt(I)]dipalladium, and highly diastereoselective lithiation to give (R)-(eta5-(Sp)-1-(alpha-N,N-dimethylaminoethyl)-2-(diphenylphosphino)cyclopentadienyl)(eta4-tetraphenylcyclobutadiene)cobalt(I) (PPCA) following the addition as electrophile of chlorodiphenylphosphine. This PN-ligand was converted into (R)-(eta5-(Sp)-1-(alpha-dicyclohexylphosphinoethyl)-2-(diphenylphosphino)cyclopentadienyl)(eta4-tetraphenylcyclobutadiene)cobalt(I), a PP-ligand (Rossiphos), by stereospecific amine-phosphine exchange using HPCy2. These air-stable P?N and P?P complexes are the first examples of a new class of bulky planar chiral ligands for application in asymmetric catalysis.

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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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Molecular mechanics analysis of structure and diastereoselectivity toward lithiation in amido- and alpha-aminoferrocene complexes

A molecular mechanics force field has been developed for the conformational analysis of amido- and aalpha-aminoferrocenes. Parameterization for ring-substituent rotational barriers in amidoferrocenes and other cross-conjugated derivatives have been calculated using DFT on both the free and complexed cyclopentadienyl ligand. Modeled structures of (diisopropylamido)- and (dimethylamido)ferrocene and N,N-dimethyl-alpha-ferrocenylethylamine are in agreement with those determined through single-crystal X-ray diffraction. The diastereo-selective lithiation of N,N-dimethylferrocenylethylamine and sparteine-mediated enantio-selective lithiation of (diisopropylamido)ferrocene using MeLi have been modeled through an assumed reversible adduct formation at the amine nitrogen or amide oxygen, followed by an irreversible ring lithiation. Results indicate that selectivity results from ring lithiation via the adduct conformer with the shortest C-Hring- – -H3C-Li interaction.

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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

Awesome Chemistry Experiments For (S)-N,N-Dimethyl-1-ferrocenylethylamine

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Substituted ferrrocenecarboxylic acids and esters

The synthesis of Fe(eta-C5H5)(eta-C5H3(CHMeNMe2)(COOH)-1,2), 3a, and its methyl and ethyl esters is described.Esterification of 3a by using RI in DMA affords Fe(eta-C5H5)(eta-C5H3(CHMeOH)(COOR)-1,2), R = Me, Et, with retention of configuration at the chiral center.The variable temperature 1H NMR spectrum of 3a reveals H-bonding between the two functional groups.

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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