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Stereochemically Controlled Bakers’-Yeast-Mediated Reductions: Synthesis of (S)-(+)-1,2-Propanediol and (S)-(-)-1,3-Butanediol, 1-Benzyl Ethers

Benzyloxyketones 1a and b can be reduced by fermenting bakers’ yeast to the corresponding protected (S)-diols 2a and b in 76 and 52percent yields, respectively (90 and >95percent e.e., respectively, as (R)-(+)-MTPA esters).

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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

Archives for Chemistry Experiments of (S)-Propane-1,2-diol

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Process for preparing enantiomerically pure propan-1,2-diols

The invention relates to a process for preparing enantiomerically pure S(+)-propan-1,2-diol and R(-)-propan-1,2-diol from L(-)-lactide or D(+)-lactide, respectively.

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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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Kinetic Resolution of 1,2-Diols with D-Camphorquinone; Preparation of (R)-(Chloromethyl)oxirane

Acid-catalysed reaction of D-camphorquinone with racemic 1,2-diols (e.g. 3-chloropropane-1,2-diol) under kinetically controlled conditions yields a predominant diastereoisomeric acetal, that can be easily converted into an optically pure epoxide.

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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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Thiolates chemically induce redox activation of BTZ043 and related potent nitroaromatic anti-tuberculosis agents

The development of multidrug resistant (MDR) and extensively drug resistant (XDR) forms of tuberculosis (TB) has stimulated research efforts globally to expand the new drug pipeline. Nitroaromatic compounds, including 1,3-benzothiazin-4-ones (BTZs) and related agents, are a promising new class for the treatment of TB. Research has shown that the nitroso intermediates of BTZs that are generated in vivo cause suicide inhibition of decaprenylphosphoryl- beta-d-ribose 2? oxidase (DprE1), which is responsible for cell wall arabinogalactan biosynthesis. We have designed and synthesized novel anti-TB agents inspired from BTZs and other nitroaromatic compounds. Computational studies indicated that the unsubstituted aromatic carbons of BTZ043 and related nitroaromatic compounds are the most electron-deficient and might be prone to nucleophilic attack. Our chemical studies on BTZ043 and the additional nitroaromatic compounds synthesized by us and others confirmed the postulated reactivity. The results indicate that nucleophiles such as thiolates, cyanide, and hydride induce nonenzymatic reduction of the nitro groups present in these compounds to the corresponding nitroso intermediates by addition at the unsubstituted electron-deficient aromatic carbon present in these compounds. Furthermore, we demonstrate here that these compounds are good candidates for the classical von Richter reaction. These chemical studies offer an alternate hypothesis for the mechanism of action of nitroaromatic anti-TB agents, in that the cysteine thiol(ate) or a hydride source at the active site of DprE1 may trigger the reduction of the nitro groups in a manner similar to the von Richter reaction to the nitroso intermediates, to initiate the inhibition of DprE1.

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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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Selective hydrogenation of lactic acid to 1,2-propanediol over highly active ruthenium-molybdenum oxide catalysts

Modification of Ru/C with a small amount of MoOx (Ru-MoOx/C) enhanced the catalytic activity in the hydrogenation of L-lactic acid to form 1,2-propanediol and maintained high selectivity. The turnover frequency based on the amount of Ru over the optimized Ru-MoOx/C catalyst (Mo/Ru molar ratio=1:16) was 114 h-1 at 393 K, which was about 4 times higher than that over Ru/C. The same effect of MoOx was obtained over Ru-MoOx/SiO2, although Ru-MoOx/SiO2 showed slightly lower activity than that of Ru-MoOx/C. Ru-MoOx/C achieved a high yield of 95 % in 18 h at 393 K and was applicable to various carboxylic acids to provide the corresponding alcohols in high yields. Modification with MoOx also brought about suppression of racemization and (S)-1,2-propanediol was obtained in high enantiomeric excess at 353 K. Based on kinetic analysis and characterization data, such as XRD, TEM, CO adsorption by a volumetric method, FTIR spectroscopy, and X-ray absorption spectroscopy, for Ru-MoOx/C and Ru-MoOx/SiO2, the catalyst structure and reaction mechanism are proposed.

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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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Asymmetric desymmetrization of 2,2?,6,6?-tetrahydroxybiphenyl through annulation with enantiomerically pure bis(mesylate)

(equation presented) 2,2?,6,6?-Tetrahydroxybiphenyl undergoes a facile annulation reaction with bis(mesylate) derived from (S)-1,2-propanediol in the presence of Cs2CO3 to give the corresponding asymmetric desymmetrization product of S axial chirality with exclusive diastereoselectivity. The desymmetrization product can be utilized as a versatile chiral building block in asymmetric synthesis of axially chiral 6,6?-disubstituted 2,2?-biphenyldiols.

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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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Novel Compounds as Cannabinoid Receptor Ligands

Disclosed herein are cannabinoid receptor ligands of formula (I) wherein A1 and Rx are as defined in the specification. Compositions comprising such compounds and methods for treating conditions and disorders using such compounds and compositions are also presented.

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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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Poly(propylene succinate): A new polymer stereocomplex

Herein we show the formation of a polymer stereocomplex by mixing isotactic, regioregular chains of poly(propylene succinate) synthesized via the copolymerization of cyclic anhydrides and epoxides. The stereocomplex exhibits significantly improved thermal properties in comparison to the enantiopure parent polymers. We demonstrate that stereocomplexation is a route to a new class of semicrystalline polyesters with improved properties, produced from readily accessible starting materials.

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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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Nano SiO2-bonded Ru-TsDPEN for catalytic resolution of 1,2-propanediol by two transfer hydrogenation

A new strategy was introduced for the catalytic resolution of 1,2-propanediol involving the successive oxidative kinetic resolution and asymmetric hydrogenation by two hydrogen transfer reactions catalyzed by nano SiO2-bonded Ru-TsDPEN [TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylene diamine]-derived catalysts composed of two opposite configurations. The catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetry-derivative thermogravimetry (TG-DTG) analysis, and inductively coupled plasma atomic emission spectrometry (ICP-AES). Results showed that Ru-TsDPEN derived catalysts were successfully grafted on the nano SiO2, affording high catalytic conversions of >99 and 99%, selectivities of 47 and 98% and maximum ee values of >99 and >99% in the two reactions, which were due to the nano SiO2 with Ru-TsDPEN in the reaction system with high dispersion. Additionally, the catalysts exhibited excellent durability and were filtered and reused at least five times without noticeable catalysts deactivations.

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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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Molecular structure of helical supramolecular dendrimers

The molecular structure of helical supramolecular dendrimers generated from self-assembling dendrons and dendrimers and from self-organizable dendronized polymers was elucidated for the first time by the simulation of the X-ray diffraction patterns of their oriented fibers. These simulations were based on helical diffraction theory applied to simplified atomic helical models, followed by Cerius2 calculations based on their complete molecular helical structures. Hundreds of samples were screened until a library containing 14 supramolecular dendrimers and dendronized polymers provided a sufficient number of helical features in the X-ray diffraction pattern of their oriented fibers. This combination of techniques provided examples of single-92 and -11 3 helices, triple-61, -81, -91, and -121 helices, and an octa-321 helix that were assembled from crownlike dendrimers, hollow and nonhollow supramolecular crownlike dendrimers, hollow and nonhollow supramolecular disklike dendrimers, and hollow and nonhollow supramolecular and macromolecular helicene-like architectures. The method elaborated here for the determination of the molecular helix structure was transplanted from the field of structural biology and will be applicable to other classes of synthetic helical assemblies. The determination of the molecular structure of helical supramolecular assemblies is expected to provide an additional level of precision in the design of helical functional assemblies resembling those from biological systems.

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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