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Density functional theory (Becke3LYP/6-311++G**) conformational analysis was carried out for all positional butanediol isomers. Taking into account the relative populations of the most stable conformers at 298.15 K, the weighted mean enthalpies of each butanediol isomer in the gas state were computed. Combining these results with the experimental values for the enthalpies of vaporization at 298.15 K, an estimate of the enthalpy of each of the butanediol isomers in the liquid state was obtained and discussed. The insight into the structural changes at the molecular level from the isolated molecule to the condensed state was improved by an infrared spectroscopy study in the OH stretching region, which was carried out for a wide range of concentrations of carbon tetrachloride solutions and pure liquids. The spectroscopic studies essentially confirmed the results derived from the combination of the computational and calorimetric studies.

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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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Arylation of K2 with Mg(C6F3H2)Br in tetrahydrofuran-dioxane and subsequent addition of either benzonitrile or dibenzylideneacetone (dba) in diethyl ether leads to the formation of labile complexes or respectively.A number of -type complexes have been prepared by addition of the corresponding neutral ligand to chloroform solutions of .Proton, 19F, and 31P n.m.r. data for all the square-planar palladium(II) complexes have been collected and 31P-<1H> spectra show that they are the cis isomers.The complex reacts with NMe4Cl to give 2 and treatment of this with the appropriate alkali-metal salt (KBr, NaI, or KSCN) leads to 2 (X = Br, I, or SCN).The behaviour of the binuclear anions in the solvents acetone and dimethyl sulphoxide has been studied by 19F n.m.r. spectroscopy.The crystal structure of 2<(C6F3H2)2Pd(mu-SCN)(mu-NCS)Pd(C6F3H2)2> has been solved and refined to R = 0.040 based on 3384 observed reflections, confirming the existence of centrosymmetric binuclear anions where the Pd atoms have square-planar co-ordination .

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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 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:
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 transformation of simple hydrocarbons into more complex and valuable products via catalytic C–H bond functionalisation has revolutionised modern synthetic chemistry. An article , which mentions category: chiral-oxygen-ligands, molecular formula is C3H8O2. The compound – (S)-Propane-1,2-diol played an important role in people’s production and life., category: chiral-oxygen-ligands

The unprecedented homogeneous hydrogenation of cyclic di-esters, in particular biomass-derived glycolide and lactide, to the corresponding 1,2-diols is catalyzed by Ru(ii) PNN (1) and Ru(ii) CNN (2) pincer complexes under mild hydrogen pressure and (in the case of 1) neutral conditions. No racemization was observed when a chiral di-ester was used. The Royal Society of Chemistry 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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The relationship between chiral centers and the helical-screw control of their peptides has already been reported, but it has yet to be elucidated in detail. A chiral four-membered ring alpha,alpha-disubstituted alpha-amino acid with a (R,R)-butane-2,3-diol acetal moiety at the gamma-position, but no alpha-chiral carbon, was synthesized. X-ray crystallographic analysis unambiguously revealed that its homo-chiral heptapeptide formed right-handed (P) and left-handed (M) 310-helical structures at a ratio of 1:1. They appeared to be enantiomeric at the peptide backbone, but diastereomeric with fourteen (R)-configuration chiral centers. Conformational analyses of homopeptides in solution also indicated that diastereomeric (P) and (M) helices existed at approximately equal amounts, with a slight preference toward right-handedness, and they quickly interchanged at room temperature. The circumstances of chiral centers are important for the control of their helical-screw direction.

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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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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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The first successful asymmetric reduction of unhindered aliphatic ketones with B-chlorodiisopinocampheylborane is reported. In contrast to the reduction in high ee of aralkyl ketones, such as acetophenone, with the reagent, the reduction of unhindered dialkyl ketones, such as 3-methyl-2-butanone, provides only poor ee. However, treatment of alpha- and beta-hydroxyketones with one equiv of diisopnocampheylborane or B-chlorodiisopinocampheylborane rapidly produces the corresponding ketoalkyl diisopinocampheylborinate intermediates, which then undergo facile intramolecular reduction. This reaction sequence, followed by oxidative workup, provides a general synthesis of 1,2- and 1,3-diols in 84?99% enantiomeric excess.

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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

Awesome and Easy Science Experiments about (S)-Propane-1,2-diol

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Eleven new chiral macrocycles (1-11, see Figure 1) of the pyridino-18-crown-6 type have been prepared.Nine diazapyridino-crown ligands contain two amide (1, R = benzyl; 4, R = phenyl), two N-methylamide (7, R = phenyl), two thionoamide (2, R = benzyl; 5, R = phenyl), two N-methylthionoamide (8, R = phenyl), two amine (3, R = benzyl; 6, R = phenyl), or two N-methylamine (9, R = phenyl) groups incorporated into the macroring.The appropriate chiral diamine was treated with dimethyl 2,6-pyridinedicarboxylate (or 2,6-pyridinedicarboxyl dichloride),O,O’-dimethyl 2,6-pyridinedicarbothioate, or 2,6-pyridinedimethyl ditosylate to prepare these materials.The macrocyclic diamides were also converted to the macrocyclic dithionoamides using Lawesson’s reagent and the latter macrocycles were reduced to the diamines.A new symmetrically substituted dimethylazapyridino-18-crown-6 ligand (10) and its N-acetyl derivative 11 were also prepared.The interactions of some of the new chiral ligands with (R)- and (S)-ammonium perchlorate were studied by 1H NMR spectral techniques.The degree of enantiomeric recognition was determined by the difference of the free energy of activation values (DeltaDeltaGexcit.) and the difference in log K values for these interactions.The X-ray analyses of the dithionoamido ligands (2, 5, and 8) showed severe deviations of the S and N atoms from the plane of the pyridine ring, especially in the case of 8.The optical rotations of 8 changed with time due to conformational changes.The relevant conformations of 8 are discussed in light of the X-ray crystallography, molecular mechanics, and 1H NMR spectra.

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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 concise total synthesis of dendrodolides A?D (1?4) has been accomplished in 10 steps from commercially available (R)-propylene oxide and 3-buten-1-ol as starting materials. The key steps involved in the synthesis are Jacobsen hydrolytic kinetic resolution, epoxide ring opening with 2-allyl-1, 3-dithiane, Yamaguchi esterification and ring-closing metathesis (RCM). In addition, a series of ester derivatives were prepared utilizing Yamaguchi esterification at the C-3 position of the dendrodolide core and screened for their efficacy against cancer cell lines.

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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