Brief introduction of (2S,3S)-Butane-2,3-diol

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Wines produced from Baga native variety from the Portuguese Bairrada Appellation, harvest 2000, were submitted to a liquid-liquid continuous extraction with dichloromethane and analysis by gas chromatography-mass spectrometry (GC-MS). A total of 53 compounds were identified and quantified. This wine has 225 mg l-1 volatile compounds, which include aliphatic and aromatic alcohols (44%), acids (27%), esters (15%), lactones (6%), amides (5%), and phenols (1%). To achieve the identification of the major would-be impact odourants, the aroma index was calculated using the concentration of each volatile component and the corresponding odour threshold reported in the literature. This methodology proved suitable, as a preliminary step, for the determination of the would-be impact odourants of Baga wine. From the 53 compounds identified, nine were determined as the most powerful odourants: guaiacol, 3-methylbutanoic acid, 4-ethoxycarbonyl-gamma-butyrolactone, isobutyric acid, 2-phenylethanol, gamma-nonalactone, octanoic acid, ethyl octanoate and 4-(1-hydroxyethyl)-gamma-butyrolactone. These data suggest Baga wine as a fruity-type product with an aroma correlated to a restricted number of compounds.

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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 chimeric (2S, 3S)-butanediol dehydrogenase (cLBDH) was engineered to have the strict (S)-configuration specificity of the (2S, 3S)-BDH (BsLBDH) derived from Brevibacterium saccharolyticum as well as the enzymatic stability of the (2R, 3S)-BDH (KpMBDH) from Klebsiella pneumonia by swapping the domains of two native BDHs. However, while cLBDH possesses the stability, it lacks the specificity. In order to assist in the design a BDH having strict substrate specificity, an X-ray structural analysis of a cLBDH crystal was conducted at 1.58 A. The results obtained show some readily apparent differences around the active sites of cLBDH and BsLBDH. Based on this structural information, a novel (2S, 3S)-BDH having a preferred specificity was developed by introducing a V254L mutation into cLBDH. The influence of this mutation on the stability of cLBDH was not evaluated. Nevertheless, the technique described herein is an effective method for the production of a tailor-made BDH.

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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 highly enantioselective catalytic double-Michael addition reaction of substituted benzofuran-2-ones with divinyl ketones promoted by readily accessible tertiary amine-thiourea Cinchona alkaloids has been developed. A number of optically enriched spirocyclic benzofuran-2-ones were prepared in very good yields (up to 99 %), diastereoselectivities (up to 19:1 d.r.), and very good enantioselectivities (up to 92 % ee). Density functional theory (DFT) calculations were performed to investigate the origin of stereoselectivity. A double take: A highly enantioselective catalytic double-Michael addition reaction of substituted benzofuran-2-ones with divinyl ketones promoted by readily accessible tertiary amine-thiourea Cinchona alkaloids has been developed. A number of optically enriched spirocyclic benzofuran-2-ones were prepared in very good yields (up to 99 %), diastereoselectivities (up to 19:1 d.r.), and very good enantioselectivities (up to 92 % ee).

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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 tris(cyanoethyl)phosphine (tcep) complexes trans-[PtCl2(tcep)2], cis-[PtMe2(tcep)2], and trans-[PtMeCl(tcep)2] are prepared by treatment of the corresponding [PtXY(cod)] (cod = 1,5-cyclooctadiene) with tcep. Reduction of trans-[PtCl2(tcep)2] with NaBH4 gives trans-[PtHCl(tcep)2] which, in the presence of tcep and NEt3, gives the coordinatively unsaturated platinum(0) complex [Pt(tcep)3]. This coordinatively unsaturated species is also formed when [Pt(norbornene)3] reacts with tcep. [Pt(tcep)3] is very unreactive compared to its PEt3 analogue: it is air-stable and does not react with further tcep to form an 18-electron species. It is protonated by HBF4 · OEt2 to form [PtH(tcep)3]BF4. The complex trans-[PdCl2(tcep)2] is made from [PdCl2(NCPh)2] and tcep and the derivatives trans-[PdX2(tcep)2] (X = Br or I) are made by metathesis of the dichloro complex. Reduction of trans-[PdCl2(tcep)2] with LiOMe in the presence of tcep gave the palladium(0) complex [Pd(tcep)3] which, like its platinum(0) analogue, undergoes exchange with free tcep on the NMR timescale. The palladium complex reacts with dibenzylideneacetone (dba) to form [Pd(eta2-dba)(tcep)2]; the same product is formed in the reaction of [Pd(eta2-dba)2] and tcep. Reaction of [Pd2Cl2(eta3-C3H3) 2] and tcep gives [PdCl(tcep)(eta3-C3H3)] or [Pd(tcep)2(eta3-C3H3)]Cl depending on stoichiometry. The rhodium(I) and iridium(I) complexes trans-[MCl(CO)(tcep)2], [MCl(tcep)(cod)] and [MCl(tcep)3] are all readily made from tcep and an appropriate precursor. All new compounds have been fully characterised by a combination of elemental analysis, IR, 31P, 13C, 1H and 195Pt NMR spectroscopy. The crystal structure of [IrCl(tcep)3] as a MeCN solvate shows a distorted square planar coordination geometry (trans angles at Ir(I) ca. 164, cis P-Ir-P av. 96, cis P-Ir-Cl av. 85). Analysis of the conformations of tcep ligands in this and other published tcep complexes shows there is a preference for conformations in which aaa, aag or g+g- (a = anti, g = gauche) arrangements of the three M-P-C-C chains are avoided.

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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 infrared and vibrational circular dichroism (VCD) spectra of six chiral oxorhenium(V) complexes, bearing a hydrotris(1-pyrazolyl)borate (Tp) ligand, have been investigated. These complexes are promising candidates for observation of parity violation (symmetry breaking due to the weak nuclear force). New chiral oxorhenium complexes have been synthesized, namely, [TpReO(eta 2-O(CH3)CH2CH2O-O,O)] (4a and 4b) diastereomers and [TpReO(eta2-N(CH3)CH 2CH2O-N,O)] (5) and [TpReO(eta2-N(tBu)CH 2CH2O-N,O)] (6) enantiomers. All compounds could be obtained in enantiomerically pure form by using either column chromatography or HPLC over chiral columns. VCD spectroscopy of these compounds and of [TpReO(eta2-N(CH3)CH(CH3)CH(Ph)O-N,O)] (2) and [TpReO(eta2-N(CH2)3CHCO2-N,O)] (3) (with chiral bidentate ligands derived, respectively, from ephedrine and proline) were studied. This allowed the absolute configuration determination of all compounds together with their conformational analysis, by comparing calculated and experimental spectra. This is the first VCD study of rhenium complexes which further demonstrates the applicability of VCD spectroscopy in determining the chirality of inorganic 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 reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus was studied using the methods of NMR, UV spectroscopy, and X-ray powder diffraction. The products of the reaction are shown to be palladium phosphides, their composition depending on the ratio of the reagents. The mechanism of the formation of the palladium-enriched phosphides is suggested, which includes the formation of palladium diphosphide PdP2 that subsequently reacts with the excess of bis(dibenzylideneacetone)palladium(0) leading to palladium phosphides Pd5P2, Pd3P0.8, Pd 4.8P, and free dibenzylideneacetone. Pleiades Publishing, Ltd., 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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This type of reactivity has quickly become one of the cornerstones of modern catalysis .In a patent, HPLC of Formula: C3H8O2, name is (S)-Propane-1,2-diol, belongs to chiral-oxygen-ligands compound, introducing its new discovery. HPLC of Formula: C3H8O2

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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A quinazoline compound of the formula (I): STR1 wherein Z means a group of the formula: STR2 (X is CH2, CHOH, CHOCH3, or O, and n is 1 to 3), or a group of the formula: STR3 (A is H or CH3, and B is –CH2 OH, or ethyl having 1 or 2 OH, or propyl having 2 or 3 OH), or a salt thereof, which are useful as anti-tumor agent, and a pharmaceutical composition containing the compound as an active ingredient.

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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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New 6-amino and 6,8-diamino-2-aryl-2,3-dihydro-4-styryl-1H- pyrimido[4,5-b][1,4]diazepines were obtained in the reaction of 2,4,5,6-tetraaminopyrimidine 1a and 4,5,6-triaminopyrimidine 1b with one equivalent of the diarylideneacetones 2 in absolute ethanol with acetic acid as the catalyst. Structure analysis of 6-amino and 6,8-diamino-2-aryl-2,3-dihydro-4-styryl-1H- pyrimido[4,5-b][1,4]diazepines 3a-i, determined by detailed nmr measurements, reveals a high regioselectivity of this reaction.

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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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Chemo-enzymatic cascade processes are invaluable due to their ability to rapidly construct high-value products from available feedstock chemicals in a one-pot relay manner. category: chiral-oxygen-ligands, Name is (S)-Butane-1,3-diol. In a document type is Article, introducing its new discovery., category: chiral-oxygen-ligands

Highly stereoselective N-acyliminium ion coupling reactions of beta-ketoester derived silyl enol ethers with enantiopure lactams derived from (S)-malic acid are reported. This reaction type is applied in the synthesis of the enantiopure C-2 substituted lactam 27, a plausible intermediate in a projected synthesis of ptilomycalin A.

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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