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This article describes the palladium-catalysed three-component coupling of 1,3-dicarbonyl compounds with nucleophiles and propargylic electrophiles for the generation of quaternary all-carbon centres in a single step, which necessitates the simultaneous control of regio-, chemo- and enantioselectivity. The use of propargyl enol carbonates, the source of two of the components, was found to be essential in maintaining high levels of regiocontrol and chemoselectivity, whereas a careful analysis of p K a trends of O-, C- and N-nucleophiles as the other coupling partner indicates that the highest levels of selectivity are likely to be obtained with relatively acidic species, such as phenols, 1,3-dicarbonyl compounds and aromatic N-heterocycles. Finally, studies towards the development of the catalytic enantioselective construction of quaternary all-carbon centres by means of alkenylation and allylic alkylation are disclosed.

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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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With the aim to explore the multifunctional behaviors of curcumin analogs and to discover new small molecular tissue factor inhibitors, twelve mono carbonyl curcumin analogs of three classes were synthesized and their effect on tissue factor procoagulant activity was evaluated in the human monoblastic leukemia THP-1 cells stimulated by LPS. The most potent compounds 2a exhibited the dramatically enhanced activity with the IC50 values of 0.053 nM. Their preliminary structure-activity relationship was also 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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An exo-selective one-pot synthesis of novel spiro[cyclohexanone-pyrandione] derivatives through two sequential organobase-catalysed 1,4-conjugate additions of pyran-2,4-dione precursors on diarylideneacetone derivatives is described. The resulting 7,11-diaryl-2-oxaspiro[5.5]undec-3-ene-1,5,9-triones were obtained as a 2:1 mixture of exo- and endo-diastereomers and adopt a meso-form due to the bilateral symmetry existing in the scaffold. Chiral-HPLC, NMR and single-crystal X-ray diffraction (including synchrotron data) have been used to elucidate the spiro[cyclohexanone-pyrandione] structure, showing therefore the exo/endo-diastereomers obtained in a meso-form, the cis-7,11-diaryl configuration (equatorial position) and different conformational changes in the cyclohexanone skeleton both in liquid and solid states. DFT studies proved the exo-stereoselectivity of the reaction by determining the exo/cis equatorial-equatorial configuration as the most thermodynamically stable form of our spiro[cyclohexanone-pyrandione] skeleton, while the structural substitution has no effect.

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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 unprecedented substituent-controlled chemoselective cleavage of C = C double bond or C(sp2)-C(CO) bond along with aerobic phosphorylation of alpha,beta-unsaturated carbonyl compounds with H-phosphonates through a radical process has been disclosed. The current strategy provides an access to beta-ketophosphonates under mild conditions with a wide substrate scope.

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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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Organocatalytic stereospecific vicinal dicholorination of a wide variety of functionalized olefins such as ketoesters, esters, ketones, carvone, cholesterol and ethyl sorbate (27 examples) was achieved using inexpensive sulfuryl chloride as well as a simple phosphine catalyst under mild reaction conditions. The products were obtained with good to excellent yields and diastereoselectivities (up to 96% yield and >25 : 1 dr).

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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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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:
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 novel and efficient method has been developed for the chemoselective conjugate reduction of alpha,beta-unsaturated ketones with tosylhydrazine as a hydrogen source to the corresponding saturated ketones in moderate to good yields. The present protocol does not require the use of transition metal, and is efficient being applicable to a wide range of substrates (25 examples).

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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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Silica chloride serves as a useful catalyst in the cross-aldol condensation, leading to the synthesis of a wide variety of bisarylidene cycloalkanones and chalcones. The catalyst showed high selectivity; self-condensation of ketones was not 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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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:
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 domino reaction of phthalhydrazide and vinylketone in the presence of phosphotungstic acid was successfully established, and 3D turbine-type tetrasubstituted 1H-indazolo[1,2-b]phthalazinedione derivatives were conveniently obtained with moderate to excellent yields (up to 95%). The highly efficient catalytic system exhibited broad substrate scopes under mild conditions. A 78% yield of the desired product was obtained when the reaction was conducted on a multi-gram scale.

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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