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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:
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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Conjugate addition reactions of organometallic compounds to electron-poor olefins is a versatile synthetic methodology for the formation of new carbon-carbon bonds. However, a careful control of the regioselectivity of the process is needed because of the presence of two electrophilic sites in the activated olefin. This issue is often overcome by employing “soft” nucleophiles such as organocopper and organozinc reagents, because of their high selectivity towards the 1,4-addition. In contrast, organolithium compounds, which are “hard” nucleophiles, generally give access to 1,2-adducts, 1,4-conjugate addition being sometimes observed according to the nature of nucleophiles and/or electrophiles, or to the presence of additives. In this Minireview, we have described some peculiar examples to get an outline of the recent acquisitions in the field of the conjugate additions of functionalized organolithiums to electron-poor olefins. Particular attention is paid to the synthesis of complex structures starting from simple substrates by means of cascade reactions promoted by conjugate addition reactions with organolithiums.

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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 typical design of chiral electroactive materials involves attaching chiral pendants to an electroactive polyconjugated backbone and generally results in modest chirality manifestations. Discussed herein are electroactive chiral poly-heterocycles, where chirality is not external to the electroactive backbone but inherent to it, and results from a torsion generated by the periodic presence of atropisomeric, conjugatively active biheteroaromatic scaffolds, (3,3-bithianaphthene). As the stereogenic element coincides with the electroactive one, films of impressive chiroptical activity and outstanding enantiodiscrimination properties are obtained. Moreover, chirality manifestations can be finely and reversibly tuned by the electric potential, as progressive injection of holes forces the two thianaphthene rings to co-planarize to favor delocalization. Such deformations, revealed by CD spectroelectrochemistry, are elastic and reversible, thus suggesting a breathing system. A jolt upon recognition: Torsion in the electroactive backbone endows poly-heterocycle films with high chiroptical activity, which is reversibly tunable by the electric potential, and outstanding enantiorecognition capability with about 100 mV between two enantiomeric ferrocenyl amino probes, in any order, in alternating sequences, and as a racemate.

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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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Dilithiation of Fe(C5H4CHMeNMe2)(C5H5) (1) with BuLi is predominantly homoannular but with BuLi/TMED is heteroannular. Heteroannular dilithiation predominates in the reaction of BuLi/TMED with Fe(C5H3(CHMeNMe2)SiMe3-1,2)(C 5H5), Fe(C5H3(CHMeNMe2)SiMe 3-1,2)(C5H4SiMe3), and Fe(C5H2(CHMeNMe2) (SiMe3)2-1,2,3,)(C5H4SiMe 3) (11). The lithioferrocenes react with ClSiMe3 to afford isolable products although some mixtures of isomers are difficult to characterize. The [3]ferrocenophane Fe(C5H3(CHMeNMe2)S3-1,2,3)(C 5H4) is obtained from 1 as are [Fe(C5H5)(C5H3(CHMeNMe 2)-1,2)]xQ (x = 2, Q = PPh; x = 1, Q = SMe; x = 1, Q = PPhCMe3 (only one diastereomer because of strong chiral induction)) and Fe(C5H4CHMeNMe2)(C5H 4AsPh2). Crystals of 11 are monoclinic: a = 17.800 (2) A, b = 11.760 (1) A, c = 13.931 (2) A, beta = 107.142 (5), Z = 4, space group P21/n. The structure was solved by conventional heavy-atom methods and was refined by full-matrix least-squares procedures to R = 0.054 and Rw = 0.061 for 2745 reflections with I ? 3sigma(I).

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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

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

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As an important bridge between the micro and macro material world, chemistry is one of the main methods and means for humans to understand and transform the material world. 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-ligandsCatalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. In an article, authors is Ori, Aiichiro, once mentioned the new application about category: chiral-nitrogen-ligands.

A chiral ferrocenylboronic acid 1 bearing an intramolecular tertiary amine binds saccharides at ca. pH 7, the complexation event, which can be conveniently detected by an electrochemical method, shows chiral discrimination for certain linear saccharides.

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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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One-pot reaction of FcCH(R)OH with equimolar quantities of BunLi and EtOCOCl followed by an excess of amine produces N-(alpha-ferrocenylalkyl)amines in up to 98% yields. Nitrogen heteroaryl amines undergo the alpha-ferrocenylalkylation at the amino group. The alpha-ferrocenylalkylation of alcohols and phenols (R’OH) leads to a formation of ethers FcCH(R)OR? in lower yields. The reactions proceed via an intermediate formation of alpha-ferrocenylalkyl carbonates FcCH(R)OCOOEt. The side reactions associated with this protocol 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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Application In Synthesis of (+)-Sparteine, Chemo-enzymatic cascade processes are invaluable due to their ability to rapidly construct high-value products from available feedstock chemicals in a one-pot relay manner. 492-08-0, Name is (+)-Sparteine,introducing its new discovery.

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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A series of new copper complexes containing chiral ferrocenyl diphosphine ligands of the Josiphos family have been prepared. These complexes have been studied in the catalytic asymmetric 1,2-addition of Grignard reagents to enones and aromatic ketones. Variation of the electronic and steric properties of the ligand resulted in a positive effect in the regio- and enantioselectivity of Grignard reagents to alpha-H-substituted enones using the ligand in which tert-butyl substituents were introduced in the diarylphosphine moiety. The copper complexes were also successfully applied in the catalytic asymmetric conjugate addition of Grignard reagents to enoates. No increase of enantioselectivity was observed in the catalytic asymmetric addition of linear Grignard reagents, compared to that of the commercially available ligand rev-Josiphos. The Royal Society of Chemistry 2014.

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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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Conjugate addition reactions of organometallic compounds to electron-poor olefins is a versatile synthetic methodology for the formation of new carbon-carbon bonds. However, a careful control of the regioselectivity of the process is needed because of the presence of two electrophilic sites in the activated olefin. This issue is often overcome by employing “soft” nucleophiles such as organocopper and organozinc reagents, because of their high selectivity towards the 1,4-addition. In contrast, organolithium compounds, which are “hard” nucleophiles, generally give access to 1,2-adducts, 1,4-conjugate addition being sometimes observed according to the nature of nucleophiles and/or electrophiles, or to the presence of additives. In this Minireview, we have described some peculiar examples to get an outline of the recent acquisitions in the field of the conjugate additions of functionalized organolithiums to electron-poor olefins. Particular attention is paid to the synthesis of complex structures starting from simple substrates by means of cascade reactions promoted by conjugate addition reactions with organolithiums.

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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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Ferrocenyltrithiocarbonates (I) are readily obtained by treating alpha-ferrocenylcarbinols (II) successively with sodium hydride, carbon disulfide and alkyl halide.Formation of I occurs by intramolecular nucleophilic displacement of oxygen by sulfur with retention of configuration.This is supported by the nature of the other products formed and by the X-ray structure determination of an optically active compound I, which was refined to R = 0.038.The title compound of R configuration was obtained from (R)-ferrocenylmethylmethanol.

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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