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A zirconium borohydride piperazine complex (Ppyz)Zr(BH4) 2Cl2, obtained by the reaction of an ethereal solution of ZrCl4 and LiBH4 with piperazine is a stable, selective and efficient reducing agent. (Ppyz)Zr(BH4)2Cl 2 reduces aldehydes, ketones, silylethers, alpha, beta-unsaturated carbonyl compounds and esters. The reactions were performed in diethyl ether at room temperature or under reflux, and the yields of the corresponding alcohols were excellent. The selective reduction of aldehydes in the presence of ketones and complete regioselectivity in the reduction of alpha,beta-unsaturated carbonyl groups were observed.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A series of cis and trans 2,6-diarylthian-4-one hydrazone derivatives (11-16) have been synthesized and characterized by 1H, 13C and two dimensional NMR spectroscopy. For the 2r,6t-diphenylthian-4-one N-isonicotinoylhydrazone (14) X-ray diffraction have also been recorded. The coupling constants suggested that the cis-hydrazones (11-13), which have the phenyl groups in cis orientation, largely exist in chair conformations with equatorial orientation of the phenyl groups 11C. Analysis of the vicinal coupling constants of trans-hydrazones (14-16) suggests that boat forms 14B must make significant contributions to it and the relative population is 58%. Moreover, in solution chair conformations 14C and 14C?, may contribute to 14. The NOESY and X-ray diffraction of 14 gives definite evidence for the contribution of 14C.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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(Chemical Equation Presented) The regiospecific [5C+1C] annulation of readily available R-alkenoyl ketene (S,S)-acetals 1 with aryl methyl ketones 2, the less active methylene compounds, has been developed. Upon treatment of 1 with 2 in the presence of t-BuOK inDMFat room temperature, highly substituted 2-cyclohexenones 3 were synthesized in high to excellent diastereoselectivities with high yields. On the basis of this strategy, sterically hindered benzophenones 4 were conveniently prepared via the iodonationaromatization of 2-cyclohexenones 3 with I2 in MeONa/MeOH basic medium. Furthermore, benzophenones 4 were also obtained directly from 1 and 2 following a sequential [5 + 1] annulation-iodonation-aromatization procedure in a one-pot operation.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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This work reports a simple and highly efficient protocol for chemoselective transfer hydrogenation of alpha,beta-unsaturated carbonyls using immobilized palladium metal-containing ionic liquid as a versatile heterogeneous catalyst with an excellent conversion and chemoselectivity (up to 100 %). The influence of various reaction parameters such as the effect of hydrogen donor, solvent, temperature, and time were studied. The catalyst was recycled for four consecutive cycles without significant loss in the catalytic activity. The developed protocol is more advantageous due to the use of HCOONH4 as a hydrogen source, mild reaction conditions, and simple workup procedure and applicable for a wide range of substrates.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The reaction of Co(eta3-C8H13)(eta4-C8H12) and Pt2(dba)3 (dba = bis-dibenzylidene acetone) under dihydrogen leads in the presence of poly(vinylpyrrolidone) to nanometric bimetallic particles CoxPt1-x. The composition of the material is determined by the initial ratio of the two organometallic precursors. The bimetallic character of the particles is evidenced by magnetic, structural, and spectroscopic studies. Structural changes are evidenced both by HREM and WAXS: platinum rich particles adopt a fcc crystalline structure while cobalt rich particles adopt a non periodic polytetraedral arrangement. The magnetic properties of the materials have been inves-tigated. ZFC/FC measurements show that the particles are superparamagnetic and that their size dispersity is very low. From isothermal magnetization measurements, the extrapolated value of the coercive field HC (T = 0) is shown to increase continuously with Pt concentration, which is characteristic of bimetallic particles.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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An effective double Michael reaction has been disclosed to access spirocyclic oxindoles in high yields (up to 98%) and excellent enantioselectivities (up to 98% ee).

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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The complexes Ru2(CO)6(mu-H)(O=C(CH=CHPh)C(H)=CPh) (5), Ru3(CO)8-(O=C(CH=CHPh)C(H)=CPh)2 (6), and Ru3(CO)7(O=C(CH=CPh)C(H)=CPh)-(O=C(CH2-CH 2Ph)C(H)=CPh) (7) were obtained in the reaction of Ru 3(CO)12 with dibenzylideneacetone PhCH=CHCOCH=CHPh. The structures of complexes 5 and 6 were established by NMR and IR spectroscopy and elemental analysis. The structure of complex 7 was established by X-ray diffraction. The structural and spectroscopic features of the complexes, as well as their possible formation and interconversion pathways are discussed.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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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:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Poly(N,N’-dibromo-N-ethyl-benzene-1,3-disulfonamide) [PBBS] and N,N,N’,N’-tetrabromobenzene-1,3- disulfonamide[TBBDA] were used as efficient reagents for conjugate addition of indole and pyrrole with a,b-unsaturated ketones and also, double-conjugate 1,4-addition of indoles to dibenzylidenacetones. Iranian Chemical Society 2012.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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An efficient Michael addition reaction of differently substituted enones with carbon, sulfur, oxygen, and nitrogen nucleophiles has been achieved by a new heterobimetallic “Pd-Sn” catalyst system. The nature of the catalytically relevant species and their interactions with the enone moiety has been examined by spectroscopy. The effect of ligand and the coordination mode of enone with “Pd-Sn” heterobimetallic system have been investigated by kinetics and DFT studies. A straightforward application of this methodology is shown in the synthesis of 1,4-oxathiepane core.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate