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Determination of the intrinsic noncovalent interactions governing chiral recognition in diastereomeric complexes constitutes the basis for understanding information transfer between molecules in living systems as well as in synthetic supramolecular structures. The most important experimental methodologies so far employed for this task are illustrated in the present review. Emphasis is put on the principles and the applications of techniques, such as radiolysis, Fourier transform ion cyclotron resonance (FTICR) and collision-induced dissociation (CID) mass spectrometry, and resonance-enhanced multiphoton ionization time-of-flight (REMPI-TOF) spectroscopy, that allow measurement of the relative stability of diastereomeric ion/molecule and molecule/molecule complexes and quantification of the short-range forces controlling their enantioselective evolution to products. (C) 2000 Elsevier Science B.V.

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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 straightforward and versatile method for the determination of the absolute configuration of vic-amino alcohols is proposed. The proposed method involves the in situ formation of chiral complexes of optically active ephedrine- or adrenaline-type vic-amino alcohols with the achiral dimolybdenum tetraacetate [Mo2(OAc)4] acting as an auxiliary chromophore. The resulting CD spectra are suitable for the assignment of absolute configuration, since the observed sign of Cotton effects arising within the d-d absorption bands for the metal cluster depends solely upon the chirality of the amino alcohol ligand. An empirically based rule correlating a positive/negative helicity expressed by the O-C-C-N torsional angle with the sign of Cotton effects occurring in the 400-260 nm spectral range has been formulated.

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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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N,N’-dimethyl-4,4′-azopyridinium methyl sulfate (MAZP) was characterized as an electron transfer mediator for oxidation reactions catalyzed by NAD+- and pyrroloquinoline quinone (PQQ)-dependent alcohol dehydrogenases. The bimolecular rate constant of NADH reactivity with MAZP was defined as (2.2 ± 0.1) × 105 M?1 s?1, whereas the bimolecular rate constant of reactivity of the reduced form of PQQ-dependent alcohol dehydrogenase with MAZP was determined to be (4.7 ± 0.1) × 104 M?1 s?1. The use of MAZP for the regeneration of the cofactors was investigated by applying the electrochemical oxidation of the mediator. The total turnover numbers of mediator MAZP and cofactor NADH for ethanol oxidation catalyzed by NAD+-dependent alcohol dehydrogenase depended on the concentration of the substrate and the duration of the electrolysis, and the yield of the reaction was limited by the enzyme inactivation and the electrochemical process. The PQQ-dependent alcohol dehydrogenase was more stable, and the turnover number of the enzyme reached a value of 2.3 × 103. In addition, oxidation of 1,2-propanediol catalyzed by the PQQ-dependent alcohol dehydrogenase proceeded enantioselectively to yield L-lactic acid.

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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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Syntheses of optically active acetylenic analogs of abscisic acid are described. The key step involves the diastereoselective alkylation of the (2S,3S)-butanediol ketal of oxoisophorone, which produces a 3:1 mixture of separable diastereoisomers. The absolute stereochemistry of the analogs was established by conversion to a known derivative and by correlation of ORD 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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The L-2,3-butanediol dehydrogenase produced in E. coli JM109/pLBD2-CTC was purified by 5 steps. The molecular mass of this enzyme was estimated at 110 kDa and the subunit was measured to be 30 KDa. The L-BDH had some differences from the BDHs from other sources in substrate specificity, pI value, pH stability, effects of divalent cations, and organic acids.

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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 compound represented by the formula I STR1 wherein X is independently both F or both Cl or one X is independently F and the other is independently Cl; R1 is a straight or branched chain (C3 to C8) alkyl group substituted by one or two groups convertible in vivo into hydroxy moieties, (e.g., a polyether ester, amino acid ester or phosphate ester) thereof or a pharmaceutically acceptable salt thereof and pharmaceutical compositions thereof useful for treating and/or preventing fungal infections are disclosed.

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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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Glycerol dehydrogenase (GDH, EC 1.1.1.6, from Enterobacter aerogenes or Cellulomonas sp.) catalyzes the interconversion of analogues of glycerol and dihydroxyacetone.Its substrate specificity is quite different from than of horse liver alcohol dehydrogenase (HLADH), yeast alcohol dehydrogenase, and other alcohol dehydrogenases used in enzyme-catalyzed organic synthesis and is thus a useful new enzymic catalyst for the synthesis of enantiomerically enriched and isotopically labeled organic molecules.This paper illustrates synthetic applications of GDH as a reduction catalyst by the enantioselective reduction of 1-hydroxy-2-propanone and 1-hydroxy-2-butanone to the corresponding R 1,2-diols (ee = 95-98percent). (R)-1,2-Butanediol-2-d1 was prepared by using formate-d1 as the ultimate reducing agent.Comparison of (R)-1,2-butanediol prepared by reduction of 1-hydroxy-2-butanone enzymatically and with actively fermenting bakers’ yeast indicated than yield and enantiomeric purity were similar by the two procedures.Reactions proceeding in the direction of substrate oxidation usually suffer from slow rates and incomplete conversions due to product inhibition.The kinetic consequences of product inhibition (competitive, noncompetitive, and mixed) for practical synthetic applications of GDH, HLADH, and other oxidoreductases are analyzed.In general, product inhibition seems the most serious limitation to the use of these enzymes as oxidation catalysts in organic synthesis.

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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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Provided herein are myeloid cell leukemia 1 protein (Mcl-1) inhibitors, methods of their preparation, related pharmaceutical compositions, and methods of using the same. For example, provided herein are compounds of Formula I, (I) and pharmaceutically acceptable salts thereof and pharmaceutical compositions containing the compounds. The compounds and compositions provided herein may be used, for example, in the treatment of diseases or conditions, such as cancer.

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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 RuCl[(S,S)-Tsdpen](p-cymene) represented by a formula below and a ketone compound are placed in a polar solvent, and the resulting mixture is mixed under pressurized hydrogen to hydrogenate the ketone compound and to thereby produce an optically active alcohol:

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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

Something interesting about (2S,3S)-Butane-2,3-diol

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Intramolecular Pauson-Khand reactions of 1,6-enynes 3a-c with a methylenecyclopropane terminator and a chiral acetal moiety adjacent to the triple bond gave spiro 5a-c in good yields with a diastereoselectivity of up to 6.4:1.The major diastereomer of 5b was converted to enantiomerically pure bicyclo<3.3.0>octane-3,8-dione 8, which showed a negative peak at 287 nm in the CD curve, consistent with an assumed (5R) configuration.Keywords: Pauson-Khand reaction, intramolecular; methylenecyclopropanes, double bond activation in; spirooct-1-en-3-ones>; enentiomerically pure compounds; stereoselection.

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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