New explortion of (S)-Propane-1,2-diol

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We report a practical one-pot synthesis of dialkylammonium salts of anionic dinuclear ruthenium complexes having chelating diphosphine ligands, BINAPs and DPB, with formula of [NEt2H2][{RuCl(diphosphine)}2(mu-Cl) 3] [2a: diphosphine = 2,2?-bis-(diphenylphosphino)-1,1?-binaphthyl; 6a: 2,2?-bis(di(p-tolyl)phosphino)-1,1?-binaphthyl; 8a: 1,2-bis(diphenylphosphino)benzene]. Treatment of cationic ruthenium complexes, [RuCl(eta6-p-cymene)(diphosphine)]Cl (4) with a slight excess of NEt2H2Cl (5a) afforded 2a, 6a, and 8a in quantitative yields. Similar reactions with various dialkylammonium salts 5b-f gave the corresponding salts, [NR2H2][{RuCl(diphosphine)}2(mu-Cl) 3]. A one-pot mixture of BINAP or its derivative, [RuCl2(eta6-arene)]2, and NR2H2Cl produced salts of the anionic dinuclear complexes which can be applied as catalysts for the asymmetric hydrogenation of ketonic substrates such as acetol and methyl acetoacetate with high activity and high enantioselectivity. The anionic face-sharing bioctahedral structure of these complexes was confirmed by the X-ray analysis of 8a, which has two hydrogen bonds between two NH of the diethylammonium cation and two terminal chloro-ligands.

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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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Bovine rumen fluid was fermented anaerobically with 25 mM R-propylene glycol, S-propylene glycol, or glycerol added. After 24 h, all of the propylene glycol enantiomers and approximately 80% of the glycerol were metabolized. Acetate, propionate, butyrate, valerate, and caproate concentrations, in decreasing order, all increased with incubation time. Addition of any of the three substrates somewhat decreased acetate formation, while addition of either propylene glycol increased propionate formation but decreased that of butyrate. R- and S-propylene glycol did not differ significantly in either their rates of disappearance or the products formed when they were added to the fermentation medium. Fermentations of rumen fluid containing propylene glycol emitted the sulfur-containing gases 1-propanethiol, 1-(methylthio)propane, methylthiirane, 2,4-dimethylthiophene, 1-(methylthio)-1-propanethiol, dipropyl disulfide, 1-(propylthio)-1-propanethiol, dipropyl trisulfide, 3,5-diethy!-1,2,4- trithiolane, 2-ethyl-1,3-dithiane, and 2,4,6-triethyl-1,3,5-trithiane. Metabolic pathways that yield each of these gases are proposed. The sulfur-containing gases produced during propylene glycol fermentation in the rumen may contribute to the toxic effects seen in cattle when high doses are administered for therapeutic purposes.

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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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Aliphatic ketones, e.g., butanone, are converted nearly quantitatively to the corresponding dioxolanes (ketals) in neat (S)- or (RS)-1,2-propanediol containing dichloroacetic acid.The reactions follow the pseudo-first-order law at a given acid concentration, are inhibited by water, and proceed approximately twofold faster in (RS)-diol-O,O-d2 than in undeuterated diol.No difference in rates greater than 1percent could be detected between (S)- and (RS)-diols at identical temperatures, acid concentrations, and water concentrations.Thus, for a chiral diol molecule and the activated complex, free-energy differences are virtually the same in (S)- and (RS)-diols as solvents.Differences in interactions among identical and enantiomeric molecules, if any, are evidently matched by differences in the activated complexes.

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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 invention relates to a method for converting a precatalyst complex to an active catalyst complex, wherein the precatalyst complex and the active catalyst complex comprise a ruthenium atom and an optically active ligand that is insoluble in water, and the active catalyst complex furthermore comprises a monohydride and a water molecule. The method comprises the steps of providing water as an activation solvent system with a pH value equal or below 2, and solving said precatalyst complex, an acid, and hydrogen therein. The invention further relates to a method for manufacturing a catalyst composition, a method for hydrogenating a substrate molecule and a reaction mixture.

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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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Vibrational Circular Dichroism combined with FTIR spectroscopy (VCD-IR) is demonstrated as a viable tool for the in situ measurement of enantiomeric excess during asymmetric catalytic transformations. Employing the Jacobsen (salen)Co-catalyzed hydrolytic kinetic resolution of racemic epoxides as a proof-of-concept case study, methodology is developed to monitor the enantiomeric excess of the epoxide substrate as a function of conversion of the limiting reactant, water. Comparison of results for monomeric and oligomeric catalysts probes the molecularity of the catalyst by investigating nonlinear effects in catalyst enantiopurity. These results are in excellent agreement with previous mechanistic investigations of this reaction based on kinetic measurements and computational 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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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

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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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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

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One of the oldest and most widely used commercial enzyme inhibitors is aspirin, which selectively inhibits one of the enzymes involved in the synthesis of molecules that trigger inflammation. you can also check out more blogs about4254-15-3 . category: chiral-oxygen-ligands

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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We report here a simple, facile, and direct nonempirical protocol for determining the absolute stereochemistry of a variety of chiral 1,2-diols and amino alcohols at room temperature with no chemical derivatization using Mg(II)bisporphyrin as a host. Addition of excess substrates resulted in the formation of a 1:2 host-guest complex in which two substrates bind in an unusual endo-endo fashion because of interligand H-bonding within the bisporphyrin cavity leading to the formation of a unidirectional screw in the bisporphyrin moiety that allowed us an accurate absolute stereochemical determination of the chiral substrate via exciton-coupled circular dichroism (ECCD). The sign of the CD couplet has also been found to be inverted when the stereogenic center is moved by one C atom simply from the bound to an unbound functionality and thus able to discriminate between them successfully. Strong complexation of the alcoholic oxygen with Mg(II)bisporphyrin rigidifies the host-guest complex, which eventually enhances its ability to stereochemically differentiate the asymmetric center. The ECCD sign of a large number of substrates has followed consistent and predictable trends; thus, the system is widely applicable. Moreover, computational calculations clearly support the experimental observations along with the absolute stereochemistry of the chiral substrate.

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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