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The direct Michael addition of enol acetates to alpha,beta-unsaturated ketones was achieved using a combination of Lewis acid catalysts, InCl 3 and Me3SiCl, which furnished stable enol-form products that could be further transformed into functionalized 1,5-diketones by reactions with various electrophiles.

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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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Johnson-type acetals derived from dimethyl tartrate give, after opening with Me2BBr and cuprate displacement, secondary alcohols with high diastereoselectivity (>30:1). The mechanism proposed for the induction of diastereoselectivity is downstream from the ring fission. It implies a direct participation of the Lewis acid as a source of nucleophile and the stereospecific transformation of the resulting bromo acetal through an invertive and temperature-dependent process. The acetals are prepared by reaction of the desired aldehyde with dimethyl tartrate. Removal of the auxiliary is accomplished through Sml2 reduction or by an addition – elimination protocol using methoxide.

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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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Dibenzylideneacetonedibromide (1) gives three different products 2, 3 and 4, when its solution in chloroform is irradiated by electromagnetic radiation at different wavelengths. The structures of these products have been confirmed by spectral analysis or co-TLC and mixed m.p. with authentic samples.

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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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Two new chiral calix[4]arene derivatives containing tartaric acid ester moieties were synthesized. The chiral calix[4]arenes are in a ‘cone’ conformation according to NMR spectroscopy. The chiral recognition capabilities of 1-4 toward the guests, 1,2-propanediol and serine methyl ester hydrochloride (SerOMe), were investigated (1H NMR spectroscopy). The extraction properties of compounds 1 and 2 toward selected alpha-amino acid methyl esters were also studied.

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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 general procedure for synthesis of 5-phenyl-1,3-dioxane-4,6-dione derivatives is described. The synthesis involves the cycloaddition of (alpha- chlorocarbonyl)phenylketene with carbonyl compounds to generate the corresponding substituted 2-oxetanone’s which is readily transformed to the final products in one step. The 1,3-dioxane-4,6-dione is a rigid cyclic structure, and can undergo easy hydrolysis.

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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 cis- and trans-2-methyl-2-oxo-2-trityl-1,3,2-dioxaphosphorinanes were obtained in the Arbuzov reaction of 2-methoxy-4-methyl-1,3,2-dioxaphosphorinane with trityl chloride. The NMR spectra (1H, 13C and 31P) in solution indicated that trans isomer exists in the form of two noncongruent molecules and it adopts two different conformations: a halfchair and a sofa, while the cis isomer exists as the mixed half/chair-sofa conformer. The compounds crystallise as a pure chiral forms and as a racemates. The solid state structural studies show that NMR data are consistent with the single crystal X-ray analysis, but the conformation existing in the crystal structure is more complex than it can be supposed on sole NMR determination. Crystal data: cis-isomer chiral form: space group P32, a = 8.782, b = 8.782, c = 21.680, alpha = 90.00, beta = 90.00, gamma = 120.00, V = 1448.0; cis-isomer racemate: space group Pca21, a = 16.773, b = 8.491, c = 27.006, alpha = 90.00, beta = 90.00, gamma = 90.00, V = 3846.2; trans-isomer racemate: space group Cc, a = 16.133, b = 8.388, c = 16.158, alpha = 90.00, beta = 117.20, gamma = 90.00, V = 1944.8; trans-isomer chiral form: space group P 1, a = 8.397, b = 9.003, c = 14.944, alpha = 80.76, beta = 74.38, gamma = 63.31, V = 971.1).

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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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Irradiation of trans-1-benzoyl-2-trans-styrylcyclopropane (IIa) and trans-1-p-toluoyl-2-trans-styrylcyclopropane (IIb), leads to formation of cis disubstituted cyclopropanes (IIIa) and (IIIb) respectively.However, photolysis of trans-1-trans-cinnamoyl-2-phenylcyclopropane (IV) results in isomerzation of the alpha,beta-double bond to produce V.Photolysis of trans-1-trans-p-methoxycinnamoyl-2-p-methoxyphenylcyclopropane (VI), by contrast, produces only a cyclobutane dimer formulated as (VII).Irradiation of 7-phenyl-3-benzylidenespiro<2.5>octan-2-one (IXb), under identical conditions, leads to isomerisation around the C=C bond.The structural assignments are based, interalia, on 13C NMR and 1H NMR spectral data.

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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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Treatment of alpha-(dimethythiocarbamoylthio) ketones with bakers’ yeast afforded the corresponding chiral alcohols in high yields with high enentiomeric excess (in most cases, more than 96 percent ee). alpha- (Dimethylthiocarbamoylthio) aldehydes were reduced to give chiral alpha-(dimethylthiocarbamoylthio) alcohols in 69-92 percent yields with 32-63 percent ee, which were converted to chiral 1,2-epitio derivatives.

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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 present invention provides three optical resolution methods. The first aspect comprises the steps of adding an optically active bifunctional resolving reagent to a bifunctional compound to form a liquid material, precipitating crystals therefrom, and treating the crystals and the liquid material separately with an acidic material, a basic material, or a basic material and an acidic material, to obtain a pair of enantiomers of an optically active bifunctional compound. The second aspect comprises an optical resolution method by which one necessary enantiomer of a pair of enantiomers in an optically active bifunctional compound is exclusively obtained. The third aspect comprises a method for racemizing one unnecessary enantiomer of a pair of enantiomers in an optically active bifunctional compound which is formed by the optical resolution method of the present invention.

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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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We evaluated the antimicrobial activity of 25 monoketone curcuminoids (MKCs) against a representative panel of cariogenic bacteria in terms of their minimum inhibitory concentration (MIC) values. Curcumin A (10) displayed promising activity against Streptococcus mutans (MIC = 50 mug/ml) and Streptococcus mitis (MIC = 50 mug/ml) as well as moderate activity against S. sanguinis (MIC = 100 mug/ml), Lactobacillus casei (MIC = 100 mug/ml), and Streptococcus salivarius (MIC = 200 mug/ml). Results indicated higher activity of compound 10 than that of its bis-beta-diketone analog. Additionally, compounds 3a (1,5-bis(4-methylphenyl)pentan-3-one) and 7b (1,5-bis(4-bromophenyl)pentan-3-ol) were moderately active against S. mitis (MIC = 100 mug/ml) and S. salivarus (MIC = 200 mug/ml).

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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