Properties and Exciting Facts About (2S,3S)-Butane-2,3-diol

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MICRO-ORGANISM FOR THE PRODUCTION OF STEREO-SPECIFIC S, S-2,3-BUTANEDIOL

The invention relates to a genetically modified lactic acid bacterium capable of producing (S,S)-2,3-butanediol stereo specifically from glucose under aerobic conditions. Additionally the invention relates to a method for producing (S,S)-2,3-butanediol and L-acetoin using the genetically modified lactic acid bacterium, under aerobic conditions in the presence of a source of iron-containing porphyrin or a source of metal ions (Fe3+/Fe2+). The lactic acid bacterium is genetically modified to express heterologous genes encoding enzymes catalysing the stereo-specific synthesis of (S,S)-2,3-butanediol; and additionally a number of genes are deleted in order to maximise the production of (S,S)-2,3-butanediol as compared to other products of oxidative fermentation.

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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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CHIRAL INDUCTION IN A BIOMIMETIC OLEFIN CYCLIZATION

Chiral induction has been achieved during a biomimetic cyclization of a chiral perillene derivatives in maximum 76percent diastereomeric excess.The absolute configuration of the predominant products are established by X-ray diffraction study and chemical transformations.

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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 Oxiranes by Chiral Molybdenum(VI) (Oxodiperoxo) alpha-Hydroxy Acid Amide/Diol Reagents

In situ formed chiral molybdenum(VI) (oxodiperoxo) hydroxy acid amide/aliphatic diol complexes mediate the efficient kinetic resolution of simple unfunctionalized oxiranes in the presence of molecular oxygen. This method furnishes high enantiomeric yields at reasonable chemical yields for the residual chiral oxiranes.

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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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Manipulating the stereoselectivity of limonene epoxide hydrolase by directed evolution based on iterative saturation mutagenesis

Limonene epoxide hydrolase from Rhodococcus erythropolis DCL 14 (LEH) is known to be an exceptional epoxide hydrolase (EH) because it has an unusual secondary structure and catalyzes the hydrolysis of epoxides by a rare one-step mechanism in contrast to the usual two-step sequence. From a synthetic organic viewpoint it is unfortunate that LEH shows acceptable stereoselectivity essentially only in the hydrolysis of the natural substrate limonene epoxide, which means that this EH cannot be exploited as a catalyst in asymmetric transformations of other substrates. In the present study, directed evolution using iterative saturation mutagenesis (ISM) has been tested as a means to engineer LEH mutants showing broad substrate scope with high stereoselectivity. By grouping individual residues aligning the binding pocket correctly into randomization sites and performing saturation mutagenesis iteratively using a reduced amino acid alphabet, mutants were obtained which catalyze the desymmetrization of cyclopentene-oxide with stereoselective formation of either the (R,R)- or the (S,S)-diol on an optional basis. The mutants prove to be excellent catalysts for the desymmetrization of other meso-epoxides and for the hydrolytic kinetic resolution of racemic substrates, without performing new mutagenesis experiments. Since less than 5000 tranformants had to be screened for achieving these results, this study contributes to the generalization of ISM as a fast and reliable method for protein engineering. In order to explain some of the stereoselective consequences of the observed mutations, a simple model based on molecular dynamics simulations has been 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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Palladium allylic complexes with enantiopure bis(diamidophosphite) ligands bearing a cyclohexane-1,2-diamine skeleton as catalysts in the allylic substitution reaction

A series of cationic allyl palladium complexes [Pd(eta3-CH3-C3H5)(P-P)]X (X = PF6, 2a-c, 2e; and X = BPh4, 3a, 3b, 3d, 3e) and [Pd(eta3-1,3-Ph2-C3H3)(P-P)]X (X = PF6, 6b; and X = BPh4, 7a) have been prepared. The bis(diamidophosphite) ligands (P-P) contain a diazaphospholidine terminal fragment derived from (R,R)- and (S,S)-N,N?-dibenzyl- and (R,R)-N,N?-dimethyl-cyclohexane-1,2-diamines and dialcoxy bridging fragment derived from (R,R)- and (S,S)-butanediol, (R,R)-cyclohexanediol, (4R,5R)- and (4S,5S)-4,5-di(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane and (R)- and (S)-binaphthol. Complexes [Pd(eta3-CH3-C3H5l)P2]X (X = PF6, 4f, 4g; and X = BPh4, 5f), where P are monodentate diamidophosphite ligands with diazaphospholidine heterocyclic backbone obtained from (R,R)- and (S,S)-N,N?-dibenzylcyclohexane-1,2-diamine and alcoxy groups coming from (R)-phenyl-ethanol and (S)-borneol have been also prepared. Neutral palladium complexes [PdCl2(P-P)] (1a, 1c) were synthesized to prove the C2symmetry of the P-P ligand. The new compounds were fully characterized in solution by NMR spectroscopy. The X-ray crystal structure determination for 2e-(R,R,Ral,Ral;R,R) and 1a-(S,S;Sal,Sal;S,S) has been achieved. The new allyl-palladium complexes were applied in the asymmetric allylic substitution reaction of the benchmark substrate rac-3-acetoxy-1,3-diphenyl-1-propene with dimethyl malonate and benzylamine as nucleophiles in order to test their catalytic potential. The best results were obtained with the 3a-(R,R;Ral,Ral;R,R) precursor (up to 84% ee) while complexes with the e ligand derived from the (R,R)-N,N?-dimethylcyclohexane-1,2-diamine terminal fragment resulted inactive in the process. The influence of the nature and the absolute configuration of both the bridging and the terminal fragments of the bis(diamidophosphite) ligand on the asymmetric induction is discussed. A preliminary study of the anion effect (PF6?vs. BPh4-) on the activity and the enantioselectivity of the Pd-catalysed allylic substitution has also been performed.

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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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Preparation of Optically Active 1,2-Diols and alpha-Hydroxy Ketones Using Glycerol Dehydrogenase as Catalyst: Limits to Enzyme-Catalyzed Synthesis due to Noncompetitive and Mixed Inhibition by Product

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£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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Enthalpy of vaporisation of butanediol isomers

The enthalpies of vaporisation of isomers of butanediol were determined by calorimetric measurements. A Knudsen effusion cell was used for this purpose. The values of the standard enthalpy of vaporisation obtained for the different isomers were compared and significant differences were found between them.

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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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Substituted diether diols by ring-opening of carbocyclic and stannylene acetals

Reduction of malonaldehyde bis(ethylene and propylene acetals) with borane or monochloroborane produces diether diols 1 and 2 in high yield. Similar reduction of glyoxal his(ethylene acetals) has only limited utility for the preparation of tetrasubstituted triethylene glycols 3. Organotin chemistry is complementary: stannylene acetals prepared from disubstituted vicinal diols can be alkylated with half an equivalent of 1,2-dibromoethane to produce tetrasubstituted triethylene glycols 3, or with two equivalents of 2-chloroethanol to produce disubstituted triethylene glycols 4.

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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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PROCESS FOR PRODUCING OPTICALLY ACTIVE FLUOROCHEMICAL

The present invention provides a process for producing an optically active fluoro compound represented by formula (3) through reaction between a specific fluoroamine and an optically active diol; and a process for producing an optically active fluoroalcohol through hydrolysis of the optically active fluoro compound. According to the process of the present invention, such optically active fluoro compounds and optically active fluoroalcohols can be produced at high optical purity and high yield in a simple manner. Such optically active fluoroalcohols are a useful source for producing drugs, pesticides, and other functional chemicals.

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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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Hydrogenation of butane-2,3-dione with heterogeneous cinchona modified platinum catalysts: A combination of an enantioselective reaction and kinetic resolution

(R)-3-Hydroxybutan-2-one was obtained with 85-90% ee albeit in low yield by the Pt/Al2O3 cinchona catalyzed hydrogenation of butane-2,3-dione by a combination of enantioselective hydrogenation and kinetic resolution.

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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