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Propane-1,2-diols from dilactides, oligolactides, or poly-L-lactic acid (PLLA): From plastic waste to chiral bulk chemicals

The preparation of racemic or enantioenriched propane-1,2-diol from dilactides, oligolactides, or poly-L-lactic acid (PLLA) is described. The transformation is carried out as tandem reactions in MeOH, covering hydrolysis and subsequent hydrogenation by using copper chromite as a catalyst. The starting material present undesired side products of the PLLA synthesis or PLLA waste. 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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Iridium phosphine abnormal N-heterocyclic carbene complexes in catalytic hydrogen transfer reactions

Several iridium complexes bearing chelating abnormal N-heterocyclic carbenes (NHCs) are shown to be active catalysts for transfer hydrogenation of ketones or enones, dehydrative C-C coupling between primary and secondary alcohols, and dehydrogenation of benzyl alcohol to benzyl benzoate. In the transfer hydrogenation of acetophenone, abnormal NHC complexes give higher activity than a normal analogue. Dehydrative C-C coupling reactions between primary and secondary alcohols result in beta-alkylation of the secondary alcohols, using primary alcohols as the apparent alkylating reagents, and such reactions proceed with high yield and selectivity. These catalytic processes are known to involve metal-mediated temporary borrowing of hydrogen from alcohols and subsequent delivery of the hydrogen to CC and /or CO bonds.

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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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Glycosides of megastigmane and of the simple alcohols from Alangium premnifolium

From the water-soluble fraction of a methanol extract of leaves of Alangium premnifolium, two new megastigmane glycosides, alangionosides N and O, along with three known megastigmane glycosides, dendranthemoside A and alangionosides A and B, were isolated. Shimaurinosides A and B, xylopyranosyl(1?6)glucopyranosides of simple alcohols were also found to be constituents of the water-soluble fraction. Structures were determined by spectroscopic analyses.

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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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beta-Cyclomanganated 1,5-diphenylpenta-1,4-dien-3-ones and their reactions with alkynes: Routes to eta5-pyranyl- And eta5-oxocycloheptadienyl-Mn(CO)3 complexes

1,5-Diphenylpenta-1,4-dien-3-ones (4) are cyclometalated with benzylpentacarbonylmanganese to form [[1-phenyl-2-((E)-3-phenylprop-2-en-1-oyl-kappaO)]ethenyl-kappaC 1]tetracarbonylmanganese derivatives (5). Coupling of 5 with alkynes in some cases gives [4-phenyl-2-(2-phenylethenyl)pyranyl-eta5]tricarbonylmanganese complexes (6) analogous to those previously reported for beta-manganated chalcones, but in other cases an alternative cyclisation pathway subsequent to insertion of alkyne into the C-Mn bond leads to [6-oxo-4,7-diphenylcyclohepta-1,4-dienyl-1,2,3,4,5-eta]tricarbonylmanganese complexes (7). The X-ray crystal structure determination is reported for one such compound, [6-oxo-2,4,7-triphenylcyclohepta-1,4-dienyl-1,2,3,4,5-eta]tricarbonylmanganese (7a), derived from 1,5-diphenylpenta-1,4-dien-3-one and phenylacetylene. The 7-phenyl group is found to occupy the endo position, and a mechanism involving Mn-mediated aryl migration is suggested to explain this stereochemistry. The reaction of 7a with ammonium cerium(IV) nitrate gives a low yield of 2-nitro-3,5,7-triphenylcyclohepta-2,4,6-trien-1-one (9), whose structure was established by X-ray crystal structure analysis. The pyranyl complexes (6) provide the corresponding pyrylium triiodide salts (8) when demetalated with iodine.

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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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Direct Regioselective [3 + 2]-Cyclization Reactions of Ambivalent Electrophilic/Nucleophilic beta-Chlorovinyl Dithianes: Access to Cyclopentene Derivatives

The highly regioselective and operationally straightforward [3 + 2] cyclizations of beta-chlorovinyl dithianes with alpha,beta-unsaturated carbonyl compounds have been developed. This protocol provides direct access to highly functionalized cyclopentenes with perfect chemo- and regioselectivities under extremely mild reaction conditions. In particular, the unprecedented cyclization allows for the selective preparation of hydroxylated cyclopentenes.

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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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Organic reactions in subcritical and supercritical water

This review describes applications to several important organic reactions in subcritical and supercritical water.

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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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Synthesis, crystal growth and characterization of 1,5-diphenylpenta-1,4- dien-3-one: An organic crystal

1,5-Diphenylpenta-1,4-dien-3-one ( dibenzalacetone, DBA) was synthesized by a base-catalyzed aldol condensation reaction between benzaldehyde and acetone. High quality single crystals have been grown by the slow evaporation of ethanol solution and the crystal belongs to monoclinic system with centrosymmetric space group C 2/c. The DBA crystals are transparent in the entire visible region and have a lower optical cutoff at ?440 nm. It is stable up to 119 C and has a good chemical stability. The high resolution X-ray diffraction curve (DC) indicates that the specimen is free from structural grain boundaries. Molecular packing leads to a centrosymmetric arrangement resulting in zero second harmonic generation (SHG; X(2)=0) efficiency.

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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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Formation of palladium phosphides in the reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus

The reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus was studied using the methods of NMR, UV spectroscopy, and X-ray powder diffraction. The products of the reaction are shown to be palladium phosphides, their composition depending on the ratio of the reagents. The mechanism of the formation of the palladium-enriched phosphides is suggested, which includes the formation of palladium diphosphide PdP2 that subsequently reacts with the excess of bis(dibenzylideneacetone)palladium(0) leading to palladium phosphides Pd5P2, Pd3P0.8, Pd 4.8P, and free dibenzylideneacetone. Pleiades Publishing, Ltd., 2012.

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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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BOROHYDRIDE REDUCING AGENT DERIVED FROM ANION EXCHANGE RESIN : SELECTIVE REDUCTION OF alpha, beta-UNSATURATED CARBONYL COMPOUNDS.

Borohydride exchange resin (BER) exhibited selectivity in the reduction of alpha, beta-unsaturated carbonyl compounds to the corresponding unsaturated alcohols.

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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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Functionalized curcumin analogs as potent modulators of the Wnt/beta-catenin signaling pathway

Osteosarcoma is a primary bone malignancy with aggressive metastatic potential and poor prognosis rates. In our earlier work we have investigated the therapeutic potential of curcumin as an anti-invasive agent in osteosarcoma by its ability to regulate the Wnt/beta-catenin signaling pathway. However, the clinical use of curcumin is limited owing to its low potency and poor pharmacokinetic profile. In this study, an attempt was made to achieve more potent Wnt inhibitory activity in osteosarcoma cells by carrying out synthetic chemical modifications of curcumin. We synthesized a total of five series consisting of 43 curcumin analogs and screened in HEK293T cells for inhibition of beta-catenin transcriptional activity. Six promising analogs, which were 6.5- to 60-fold more potent than curcumin in inhibiting Wnt activity, were further assessed for their anti-invasive activity and Wnt inhibitory mechanisms. Western blot analysis showed disruption of beta-catenin protein nuclear translocation following treatment with analogs 2f, 3c and 4f. Using transwell assays, we also found that these compounds were more potent than 1a (curcumin) in impeding the invasion of osteosarcoma cells, possibly through suppressing MMP-9 activity. Structure-activity-relationship studies revealed that Wnt inhibitory effects could be enhanced by shortening and restraining the flexibility of the 7-carbon linker moiety connecting the terminal aromatic rings of curcumin and substituting both rings with appropriate substituents. Our results demonstrate that the synthesized curcumin analogs are more potent Wnt inhibitors in osteosarcoma cell lines as compared to parental curcumin and are good lead compounds for further development. Future in vivo tests with these compounds will define their therapeutic potentials as promising drug candidates for clinical treatment of osteosarcoma.

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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