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Palladium-catalyzed reaction of 2-iodoferrocenyl alcohols with internal alkynes: Synthesis of functionally 1,2-disubstituted ferrocenes and ferroceno-pyrans

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.

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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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A Ugi’s amine and synthetic method of derivative thereof (by machine translation)

The invention discloses a formula (I) indicated by the Ugi’s amine and its derivatives of the synthesis method, the method to ferrocene and its derivatives as raw materials, obtained by reductive amination of racemic […], then racemic […] split by the resolving agent, to a primary amine of the optical isomer, optical isomer primary amine by alkylation or reductive amination reaction shall be stated Ugi’s amine and its derivatives. The chiral Ugi’s amine and its derivatives can be used for synthesizing a series of Josiphos such ferrocene diphosphine ligand, as various metal complex catalyst of chiral ligand, is preparing a pharmaceutical intermediate, agricultural chemicals important chiral catalyst ligand, in metal catalytic asymmetric reaction have a wide range of application, and is suitable for industrial scale production. The invention mild reaction conditions, cheap raw material, the synthetic route is simple, higher yield and chiral purity. (by machine translation)

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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

More research is needed about (+)-Sparteine

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PROCESS FOR CONVERTING LUPANINE INTO SPARTEINE

The present invention relates to processes for preparing enantiopure Lupanine and Sparteine.

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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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FUNCTIONALIZED MAGNETIC NANOPARTICLE, A CATALYST, A METHOD FOR FORMING C-C BONDS

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£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

Properties and Exciting Facts About (S)-N,N-Dimethyl-1-ferrocenylethylamine

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Synthesis of derivatives of (alpha-(dimethylamino)ethyl)ferrocene via lithiation reactions and the structure of 2-(alpha-(dimethylamino)ethyl)-1,1?,3-tris(trimethylsilyl)ferrocene

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£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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Electrochemical Detection of Saccharides by the Redox Cycle of a Chiral Ferrocenylboronic Acid Derivative: a Novel Method for Sugar Sensing

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£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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Synthesis of planar chiral ferrocenyl 1,3-diamines and 1,3-amino ethers

The efficient syntheses of novel planar chiral 1,3-diamines and 1,3-amino ethers with an oxy or amino function directly bound to the cyclopentadienyl ring of ferrocene has been developed. The key reaction is the Cu2O promoted substitution of of (pR)-diisopropyl-2-iodoferrocenecarboxamide with either phthalimide or AcOH to introduce nitrogen or oxygen functionality onto the cyclopentadienyl ring. The enantiomerically pure iodoferrocene derivative is available from the known enantioselective ortho-lithiation of N,N-diisopropylferrocenecarboxamide with n-BuLi sparteine, In the course of these studies the synthesis of a novel C2 symmetric C-2 dimer of N,N-dimethyl-1-ferrocenylethylamine was characterised by single crystal X-ray diffraction.

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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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PROCESS

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£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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MASS SPECTROMETRY OF ?-COMPLEXES OF TRANSITION METALS XX. DIMETHYLAMINOALKYL DERIVATIVES OF FERROCENE AND CYMANTRENE; THE DETERMINATION OF THE DISTRIBUTION AND THE TOTAL CONTENT OF DEUTERIUM LABEL

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£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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Synthesis of tetraphenylene derivatives and their recent advances

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£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