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Formation and X-ray structure of the mu-alkylidene complex Fe2(CO)6(mu-eta3, eta3-C(CH=CHPh)2) upon deoxygenation of Fe2(CO)8(mu-eta2, eta2-C(O) (CH=CHPh)2) with methyl lithium

Di-iron nonacarbonyl reacts with dibenzylideneacetone (5) to produce, depending on the reaction conditions, either a mixture of the three complexes Fe(CO4 (6), Fe2(CO)8 (7), and Fe(CO)3 (8), or solely complex 7 in which the ligand is bound in a eta2, mu-eta2, eta2, or eta4 fashion.All three complexes have been fully characterized by X-ray crystallography.Crystal data for complex 6: C21H1 4FeO5, monoclinic, space group P21/n, a = 6.326(2) Angstroem, b = 14.567(2) Angstroem, c = 20.504(2) Angstroem, beta = 96.91(2) deg, U = 1875(4) Angstroem3, Dc = 1.42 g cm-3, Z = 4.For complex 7: C25H14Fe2O9, space group P1, a = 9.677(5) Angstroem, b = 10.635(5) Angstroem, c = 13.471(6) Angstroem, alpha = 104.24(3) deg, beta = 105.46(4) deg, gamma = 104.75(4) deg, U = 1216.7(8) Angstroem 3, Dc = 1.56 g cm-3, Z = 2.For complex 8: C20H14FeO4, orthorhombic, space group Pbca, a = 13.397(2) Angstroem , b = 10.041(3) Angstroem, c = 26.579(2) Angstroem, U = 3575.1(8) Angstroem3, Dc = 1.39 g cm-3, Z = 8.Upon reaction with MeLi under an atmosphere of CO, all of the three complexes each gave a mixture of the expected eta4-ketene complex Fe(CO)4(eta4-PhCH = CH(C=C=O)CH = CHPh) (9) as the result of a deoxygenation-carbonylation reaction, and the new mu-alkylidene complex Fe2(CO)6(mu-eta3, eta3-C(CH=CHPh)2) (10) as the result of a deoxygenation reaction of the starting complex followed by the trapping of the intermediate alkylidene complex by Fe(CO)3.Complex 10, C23H14Fe2O6, has been fully characterized by X-ray crystallography and shown to be orthorhombic, space group Pbcn, a = 17.155(4) Angstroem, b = 7.842(2) Angstroem, c = 15.857(2) Angstroem, U = 2133.2(5) Angstroem3, Dc = 1.55 g cm-3, Z = 4.Keywords: Iron; Ketene; Alkylidene complexes; Dibenzylideneacetone

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Cationic Alkynyl Heck Reaction toward Substituted Allenes Using BobCat: A New Hybrid Pd(0)-Catalyst Incorporating a Water-Soluble dba Ligand

The cationic alkynyl Heck reaction between aryl triflates and alkynes to give substituted allenes is described. Key to the success of this method was the discovery and development of a new hybrid Pd(0)-catalyst, BobCat, that incorporates a water-soluble dba-ligand and biaryl phosphine ligand to provide substituted allenes in good yields under mild reaction conditions.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Asymmetric Ni-catalyzed conjugate allylation of activated enones

The nickel-catalyzed enantioselective addition of allylboronic acid pinacol ester, allylB(pin), is described. This reaction is highly effective with dialkylidene ketones and favors the allylation of the benzylidene site in nonsymmetric substrates. The reaction appears to proceed by conversion of the dialkylidene ketone substrate to an unsaturated pi-allyl complex (I), followed by reductive elimination. Enantioselectivities range from 91 to 94% ee for a range of substrates when chiral ligand 14 is employed.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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APPLICATION OF 13C NMR SPECTROSCOPY TO THE DETERMINATION OF THE BASICITY OF CARBONYL-CONTAINING COMPOUNDS

The possibilities and limitations of 13C NMR spectroscopy for the determination of the basicity of carbonyl-containing compounds are examined.It is shown that the protonation of polycyclic aromatic ketones in deutero acids increases the contribition of the C+-OD form relative to that of the C=+OD form, whereas in the case of aliphatic ketones and of monosubstituted acetophenones and benzaldehydes the C=+OD form is predominant.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Formal diels-alder reactions of chalcones and formylcyclopropanes catalyzed by chiral n-heterocyclic carbenes

Highly enantioselective (formal) hetero-Diels-Alder reactions between chalcones and formylcyclopropanes are disclosed. The challenging N-heterocyclic carbene (NHC)-bounded enolate intermediates from formylcyclopropanes were captured for new C-C bond forming reactions. The reaction products were obtained with high diastereo- and enantioselectivities and could be easily transformed to optically pure multisubstituted cyclohexane derivatives.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Transition-Metal-Catalyzed Asymmetric Organic Synthesis via Polymer-Attached Optically Active Phosphine Ligands. 6. Asymmetric Hydrogenation with Polymer Catalysts Containing Optically Active Pendent Alcohols

Three acrylate comonomers, (S,S), (R,R) and racemic 1-methyl-2-hydroxypropyl acrylate (7a-c), were prepared from the corresponding isomers of 2,3-butanediol.The acrylates were copolymerized with ethylene dimethacrylate and N-acryloyl-(2S,4S)-4-(diphenylphosphino)-2-<(diphenylphosphino)methyl>pyrrolidine (8) to give cross-linked resins containing phosphinopyrrolidines and optically active alcohols.Polymers containing the 4,5-bis<(diphenylphosphino)methyl>-1,3-dioxolane unit (DIOP) were prepared by copolymerizing acrylates 7a-c with ethylene dimethacrylate and 2-p-styryl-4,5-bis<(tosyloxy)methyl>-1,3-dioxolane (1) and treating the polymers with an excess of sodium diphenylphosphide.Exchange of Rh(I) onto these polymers provided catalysts that hydrogenated 2-acetamidoacrylic acid in tetrahydrofuran.The enantiomeric excesses obtained with the polymer-bound catalysts varied with the structure of the pendent alcohol, suggesting the participation of the polymer-bound alcohol at the catalyst site to provide an alcohol-like environment.A difference in enantiomeric excess (ee) was noted when catalysts containing either R or S alcohols were used.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Deprotection of oximes, phenylhydrazones, semicarbazones and thiosemicarbazones to the corresponding carbonyl compounds using cetyltrimethylammonium peroxodisulfate as a new and selective oxidizing agent

Cetyltrimethylammonium peroxodisulfate (CTA)2S2O 8 was quantitatively prepared and used for the deprotection of oximes, phenylhydrazones, semicarbazones and thiosemicarbazones to the corresponding carbonyl compounds in acetonitrile. Its agent is more efficient and has advantages over similar reagents in terms of the amount of oxidant, short reaction time, simple work up, and high yield.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Factors determining the chemoselectivity of phosphorus-modified palladium catalysts in the hydrogenation of chloronitrobenzenes

The precursor nature effect on the state of the Pd?P surface layer in palladium catalysts and on their properties in the liquid-phase hydrogenation of chloronitrobenzenes under mild conditions has been investigated. A general feature of the Pd?P-containing nanoparticles obtained from different precursors and white phosphorus at P/Pd = 0.3 (PdCl2 precursor) and 0.7 (Pd(acac)2 precursor) is that their surface contains palladium in phosphide form (BE(Pd3d5/2) = 336.2 eV and BE(?2?) = 128.9 eV) and Pd(0) clusters (BE(Pd3d5/2) = 335.7 eV). Factors having an effect on the chemoselectivity of the palladium catalysts in chloronitrobenzenes hydrogenation are considered, including the formation of small palladium clusters responsible for hydrogenation under mild conditions.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Highly enantioselective synthesis of spiro[cyclohexanone-oxindoles] and spiro[cyclohexanone-pyrazolones] by asymmetric cascade [5+1] double Michael reactions

The asymmetric catalytic synthesis of naturally occurring and biologically active spiro compounds is a challenge for modern chemical methodology. Here we report the construction of spiro compounds through cascade [5+1] double Michael reactions between divinyl ketones and N-unprotectedoxindoles or N-phenyl-protected pyrazolones catalyzed by a combination of the easily available 9-amino-9-deoxy-epi-quinine with N-Boc-D-phenylglycine. The desired multistereogenic spiro[cyclohexanone-oxindoles and -pyrazolones] were obtained with high yields (up to 98 %) andstereoselectivities (up to >20:1 dr, 99 % ee). An efficient approach to spiro compounds through cascade [5+1] double Michael reactions between divinyl ketones and oxindoles or N-protected pyrazolones in the presence of 9-amino-9-deoxy-epi-quinine and N-Boc-D-phenylglycine is reported. Multistereogenic spiro[cyclohexanone- oxindoles and -pyrazolones] are obtained with high yields (up to 98 %) and stereoselectivities (up to >20:1 dr, 99 % ee). Copyright

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Synthetic Route of 24621-61-2, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.24621-61-2, Name is (S)-Butane-1,3-diol, molecular formula is C4H10O2. In a article£¬once mentioned of 24621-61-2

ORGANIC COMPOUNDS

The application relates to novel substituted piperidines of the general formula (I) in which R1, R2, R3, R 4, W, X, Z, m and n are each as defined in detail in the description, to a process for their preparation and to the use of these compounds as medicines, in particular as renin inhibitors.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate