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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:
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 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:
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 mass spectrometry behaviour of dimethylaminomethyl- and alpha-(dimethyl-amino)ethyl derivatives of cymantrene and ferrocene, their iodine methylates as well as of the deutero analogues of these compounds has been studied.It has been shown that mass spectrometry can be successfully employed for the quantitative determination of the total deuterium content in aminoalkyl derivatives of cymantrene and ferrocene, the distribution of the label between the dimethylaminoalkyl group and the metallocenyl fragment and in case of the dimethylaminomethylferrocene also between thesubstituted and unsubstituted cyclopentadienyl rings.The data on the distribution of the isotopic label were used to ascertain the mechanism of fragmentation of the dimethylaminomethylferrocene under electron impact.

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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 catalyzed pathway has a lower Ea, but the net change in energy that results from the reaction is not affected by the presence of a catalyst. category: chiral-nitrogen-ligands, 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.

Reactions catalyzed within inorganic and organic materials and at electrochemical interfaces commonly occur at high coverage and in condensed media,category: chiral-nitrogen-ligands, Name is (S)-N,N-Dimethyl-1-ferrocenylethylamine, belongs to chiral-nitrogen-ligands compound, is a common compound. category: chiral-nitrogen-ligands, In an article, authors is Yucel, Baris, once mentioned the new application about category: chiral-nitrogen-ligands.

The reaction of racemic (2-iodoferrocenyl)methanol with internal alkynes in the presence of (dppf)PdCl2 and i-Pr2NH produces alkenyl-substituted ferrocene carboxaldehydes in moderate yields. All reactions are carried out at 100 or 120 C for different reaction times (between 6 and 26 h) in a screw-cap Pyrex bottle. The scope and limitations of this reaction are studied by employing variously substituted 11 internal alkynes. The reactions are regioselective with alkynes having a sterically crowded substituent such as t-butyl and trimethylsilyl groups. Moreover, racemic 1-(2-iodoferrocenyl)ethanol derivatives are synthesized as two diastereomers. Both diastereomers are reacted with internal alkynes in the presence of (dppf)PdCl2 and i-Pr2NH at 120 C to afford alkenyl-substituted acetylferrocenes and ferroceno-pyrans in moderate to good yields. According to the alkyne employed, different reaction times (between 6 and 55 h) are necessary to drive the reactions to completion. Mechanisms are also suggested for the formation of observed products.

The catalyzed pathway has a lower Ea, but the net change in energy that results from the reaction is not affected by the presence of a catalyst. category: chiral-nitrogen-ligands, 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.

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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Ferrocenyl diphosphines R2PF-P(R?)2 are effective, tunable ligands for the iridium catalyzed enantioselective hydrogenation of N-aryl imines in the presence of iodide and acid promoters. Structure-activity/selectivity correlations were found for the hydrogenation of N-(2-ethyl-6-methylphenyl)-N-(1?-methoxymethyl)-ethylidene-amine (MEA-imine) and for 2,3,3-trimethylindolenine (TMI). Extremely high catalytic activity and moderate to good enantioselectivity were observed for the MEA imine using a catalyst generated in situ from [Ir(cod)Cl]2 and (R)-(S)-PPF-P(3,5-Xyl)2 (xyliphos). With the same type of catalysts, several other N-aryl imines can be hydrogenated with enantioselectivities between 31 and 96%, albeit with lower catalyst activities.

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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 present invention provides a metallocenyl compound of formula (I). Ra, Rb, Rc, Rd, Re, Rf, M, m, n, j, k, Y and Z and * are as described in the specification. The invention also provides a process for the preparation of the complexes, a process for increasing the optical purity of a compound of formula (II) and a process for the asymmetric transfer hydrogenation (ATH) of a metallocenyl compound of formula (V) to a metallocenyl compound of formula (IV).

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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 simplified procedure for the preparation of alpha-N,N-dialkylaminoethylferrocenes R2NR’ (r=Me, C6H11, CHMe2; R’=CH(CH3)C5H4FeC5H5) from the alcohol R’OH by treatment with HBr and R2NH is described.Use of ammonia results in the isolation of R’NH2, R’2NH (major product) and R’3N and use of the optically active amine d-(+)-H2NCH(CH3)C6H5 gives rise to diastereomers R’NHCH(CH3)C6H5 which are separable.When diphenylphosphine is substituted for an amine the oxide R’P(O)Ph2 is obtained in low yield.The secondary amine R’2NH reacts with n-butyllithium and chlorodiphenylphosphine to afford R’2NHPPh2.

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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 new types of ferrocenyloxaaliphatic acid ester, FcCHROCHR?COOMe (R = H, Me, Ph; R? = H, Me) (7) have been prepared by the action of alkoxides derived from methyl glycolate or methyl lactate on the corresponding ferrocenylcarbinyl acetates (2) or N,N,N-trimethylferrocylammonium iodides (4). The esters obtained were accompanied by a small quantity of oligomeric esters, FcCHR(OCHR?CO)nOMe (9), and with more or less ferrocyl methyl ethers (8). As opposed to the alkaline hydrolysis of the analogous methyl benzoxyacetate (6) into benzoxyacetic acid (5) the acidification of sodium alkanoates 10 obtained by saponification of esters 7 gave unexpectedly the corresponding ferrocenylcarbinols 1. In a similar way the esters 7 were converted into mixtures of the mentioned carbinols and diferrocyl ethers 11 under action of aqueous hydrochloric acid. The mechanisms of the reactions 10 ? 1 and 7 ? 1, 11 are 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 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:
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 functionalized magnetic nanoparticle including an organometallic sandwich compound and a magnetic metal oxide. The functionalized magnetic nanoparticle may be reacted with a metal precursor to form a catalyst for various C?C bond forming reactions. The catalyst may be recovered with ease by attracting the catalyst with a magnet.

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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