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We describe efficient and flexible enantioselective syntheses of the active enantiomers of the pheromones of pine sawflies, including the species Diprion jingyuanensis, their homologs and, stereoisomers, as well as those identified from the Chinese species Diprion jingyuanensis, i.e., 126. A total of 48 compounds, including acetates 78-101 and propanoates 102-125, have been synthesized. Our general approach towards these compounds originated from the commercially available chirons diethyl (S)- and (R)-malates, as well as ethyl (R)-3-hydroxybutanoate. The Seebach asymmetric methylation was employed in a key step to control additional configuration. 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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A ruthenium complex was found to catalyze the hydrogen reduction of esters under mild and neutral conditions. A variety of optically active esters can be reduced to the corresponding alcohols in excellent yield without loss of their optical purity or causing undesirable side reactions. Hydrogen reduction needs such simple operations – reaction, concentration, and purification – that the violent quench step and extraction step, which accompany conventional sodium borohydride or lithium aluminum hydride reduction, can be omitted.

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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) We have designed a series of diphosphite ligands to study the effect of the backbone, the size of the chelate ring, and the substituents of the biphenyl moieties and to determine the scope of this type of ligand in the Pd-catalyzed asymmetric substitution reactions of different types of substrates. Good-to-excellent activities and enantioselectivities have been obtained for disubstituted linear substrate 11 (TOF’s up to >2000 mol × (mol × h)-1, ee values up to 99%) and cyclic substrate 14 (TOF up to 285 mol × (mol × h) -1, ee values up to 92%). However, these ligands are inadequate for the Pd-catalyzed allylic alkylation of monosubstituted linear substrates because they provide low enantioselectivities.

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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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Complexes RuCl2(ArCN)2(binap), II (binap=(R)- or (S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl; ArCN=benzonitrile, a; 2-furancarbonitrile, b; pentafluorobenzonitrile, c) were prepared, and their solution properties were investigated by 31P NMR measurements.The catalytic aactivities and enantioselectivities for IIa-c catalysed hydrogenation of some prochiral acids were very similar to those provided by Ru2Cl4(binap)2(NEt3), I.In the hydrogenation of beta-functionalized carbonyl compounds, however, IIa-c showed considerably lower activities and/or selectivities, compared with complex I.The differences in IIa-c catalysed reactions are discussed in relation to the coordinating abilities of ArCN in II.

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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 number of ether- and thioether-substituted ferrocenes (1,1?-bis(1,3-dioxane-2-yl)ferrocene 1, 1,1?-bis(5-methyl-1,3- dioxane-2-yl)ferrocene 2, 1,1?-bis(4-methyl-1,3-dioxane-2-yl)ferrocene 3, 1,1?-bis[(R)-(-)-4-methyl-1,3-dioxane-2-yl]ferrocene 4, 1,1?-bis(4,6-dimethyl-1,3-dioxane-2-yl)ferrocene 5, and 1,1?-bis(1,3-dithiane-2-yl)ferrocene 6) were synthesised by direct condensation of 1,1?-diformylferrocene with the corresponding diols or dithiols. The crystal structures of 1, 5a, 5b, and 6 were determined by X-ray diffraction studies. Electrospray ionisation mass spectrometry was used to investigate the binding behaviour of 1 and 6 toward alkali as well as transition metal cations. The dioxane-containing species 1 showed high affinity toward Li+ and Na+, whereas the dithiane derivative 6 bound, as expected, preferentially to Hg2+. The Royal Society of Chemistry 2003.

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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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Disclosed is a compound of having the formula (II-A), pharmaceutically acceptable salts or solvates thereof and pharmaceutical compositions containing the same, wherein the structural variables are as defined herein. The compounds, salts and solvates of this invention are useful as LXR agonists.

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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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Enantiomerically pure R or S 1,3-butanediols were prepared in four steps from L to D threonine by nitrous deamination in the presence of bromide ion followed by esterification and reduction.

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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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Chiral (R,R)-tartaric acid and NaBr-doubly modified Raney nickel (TA-MRNi) is a promising heterogeneous catalyst for enantioselective hydrogenation of prochiral beta-keto esters. To obtain deeper insights into the factors ruling the enantioselectivity, enantiodifferentiating hydrogenation of substituted ketones was studied over TA-MRNi and NaBr-modified RNi by use of combined individual-competitive hydrogenation techniques. Relative equilibrium adsorption constants of the substrates were estimated to evaluate their relative interaction strength with adsorbed tartaric acid moiety. DFT calculations were also performed to estimate the interaction energy through hydrogen bonding, providing clear support to the kinetic analysis and surface model. It is concluded with the enantioselective hydrogenation of ketones over TA-MRNi that the enantioselectivity increases as the substrate-modifier interaction strength increases: Methyl acetoacetate (MAA) > acetylacetone (AA) ? 4-hydroxy-2-butanone (HB) > 2-octanone (2O).

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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 diastereoselective approach to (2R,5S)- and (2S,5S)-2-methyl-1,6-dioxaspiro[4.5]decane 1 and 1a is described. The route starts with an alkylation reaction among the cyclopentanone N,N-dimethylhydrazone 6 and the chiral iodides (R)-3 or (S)-3, derived from the enantiomers of ethyl beta-hydroxybutyrate, controlling the estereocenter at C-2 of the molecules. The alkylated products 7 and 7a were easily transformed into the 1,8-O-TBS-1,8-dihydroxy-5-nonanones 9 and 9a in four steps, and a subsequent stereoselective spiroketalization, in acidic media, afforded a Z:E mixture (1:2) of compounds 1 and 1a.

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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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Ruthenium complexes of phosphinoferrocenylaminophosphine ligands (BoPhoz ligands) have been prepared by combining the ligands with tris(triphenylphosphine)ruthenium dichloride and precipitating the complexes. The optimal species exhibit high enantioselectivities for the asymmetric hydrogenation of functionalized ketones, particularly beta-ketoesters.

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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