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A series of -amino alcohols derivatives were synthesized from (R)-2-amino-1-butanol and (S)-1,2-propanediol, and they have been used as organocatalaysts in the racemic ring opening of epoxide in good yields with high enantiomeric excess (up to 97%). Copyright

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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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Birman’s HBTM catalyst is effective for the enantioselective acylation and kinetic resolution of benzylic secondary alcohols. The enantioselective acylation has now been extended to secondary alcohols bearing electron-withdrawing groups such as halides and other heteroatoms. The level of selectivity is modest to good and is sufficient for determining configuration using the competing enantioselective conversion method. A mathematical analysis identifies conditions for achieving maximum differences in conversion and, consequently, assigning configuration with greater confidence. The new method is effective for halohydrins and secondary-tertiary 1,2-diols and was used to confirm the configuration of two inoterpene natural products.

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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

Awesome Chemistry Experiments For C4H10O2

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Electric Literature of 19132-06-0, Chemical Research Letters, May 2021. The prevalence of solvent effects in heterogeneous catalysis in condensed media has motivated developing quantitative kinetic, spectroscopic. In a document type is Article, and a compound is mentioned, 19132-06-0, Name is (2S,3S)-Butane-2,3-diol, introducing its new discovery.

The cells of Bacillus stearothermophilus contain an NADH-dependent diacetyl (acetoin) reductase. The enzyme was easily purified to homogeneity, partially characterised, and found to be composed of two subunits with the same molecular weight. In the presence of NADH, it catalyses the stereospecific reduction of diacetyl first to (3S)-acetoin and then to (2S,3S)-butanediol; in the presence of NAD+, it catalyses the oxidation of (2S,3S)- and meso-butanediol, respectively to (3S)-acetoin and to (3R)-acetoin, but is unable to oxidise these compounds to diacetyl. The enzyme is also able to catalyse redox reactions involving some endo-bicyclic octen- and heptenols and the related ketones, and its use is suggested also for the recycling of NAD+ and NADH in enzymatic redox reactions useful in organic syntheses.

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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 series of chiral beta3-aminoxy acids or amides with various side chains have been synthesized via two different approaches. One is the Arndt-Eistert homologation approach, using chiral alpha-aminoxy acids as starting materials. The other approach, utilizing the enantioselective reduction of beta-keto esters catalyzed by baker’s yeast or chiral Ru(II) complexes, produces chiral beta3-aminoxy acids with nonproteinaceous side chains. The oligomers of beta3-aminoxy acids can be readily prepared using EDCI/HOAt as the coupling reagent.

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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

Can You Really Do Chemisty Experiments About (S)-Propane-1,2-diol

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Homochiral (E)- and (Z)-enamides derived from SuperQuat (S)-4-phenyl-5,5-dimethyl-oxazolidin-2-one undergo highly diastereoselective epoxidation upon treatment with dimethyldioxirane. Subsequent epoxide opening with meta-chlorobenzoic acid proceeds via a stereoselective SN1-type process, with retention of configuration, to give the corresponding 1?-m-chlorobenzoyl-2?-hydroxy derivatives. Treatment of the SuperQuat enamides with mCPBA effects this two-step transformation in one pot. Reductive cleavage of the isolated 1?-m-chlorobenzoyl-2?-hydroxy derivatives (?96% de) generates homochiral 1,2-diols in ?96% ee. Alternatively, regioselective lithiation of the enamide at C(1?) with tBuLi followed by reaction with an aromatic aldehyde and in situ O-benzylation generates a 1?-(benzyloxy-aryl-methyl) substituted enamide with high diastereoselectivity. Subsequent oxidative cleavage of the enamide C{double bond, long}C bond with NaIO4/RuCl3 followed by methanolysis of the resultant N-acyl fragment furnishes an O-benzyl protected alpha-hydroxy methyl ester in high 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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Mild and sweet: The title reaction proceeds under mild conditions with high regio- and diastereoselectivity (see scheme, PG=protecting group, DiPPF=1,1?-bis(diisopropylphosphino)ferrocene). This reaction is suitable for a wide range of glycal-derived gamma-ketone esters and affords C-glycosides with exclusive beta-selectivity. The method was further applied to a concise formal synthesis of aspergillideA. Copyright

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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 Pd-catalyzed efficient reductive cross-coupling reaction without metallic reductant to construct a Csp2-Csp3 bond has been reported. A PdIV complex was proposed to be a key intermediate, which subsequently went through double oxidative addition and double reductive elimination to produce the cross-coupling products by involving Pd 0/II/IV in one transformation. The oxidative addition from Pd II to PdIV was partially demonstrated to be a radical process by self-oxidation of substrate without additional oxidants. Furthermore, the solvent was proved to be the reductant for this transformation through XPS analysis.

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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 one-pot synthesis of palladium nanoparticles supported on magnesium hydroxide fluoride has been performed with the fluorolytic sol-gel method. The prepared catalysts were characterized by using various physicochemical techniques. The sol-gel method led to high surface area (> 135 m2g-1), mesoporous catalysts (pore volume=0.19-0.23 cm3g-1, pore diameter= 3-5 nm) with uniformly dispersed palladium nanoparticles approximately 2 nm in diameter on the surface. The catalysts synthesized by using different concentrations of aqueous hydrofluoric acid exhibited changing surface and acidic properties. Very high dispersion of palladium on magnesium fluoride (47%) was obtained with 1 wt% palladium loading. The catalysts were used for hydrogenation of various olefins in the presence of other organic functionalities at room temperature and atmospheric hydrogen pressure. Various substituted olefins were hydrogenated with almost 100% conversion and selectivity. The catalysts were recycled efficiently over five cycles without appreciable loss in catalytic activity. There was no palladium leaching under the reaction conditions, which was confirmed by inductively coupled plasma atomic emission spectroscopy analysis. Activation of olefin on the catalyst surface could not be observed by in situ FTIR studies, indicating facile activation of hydrogen on the palladium supported on magnesium hydroxide fluoride.

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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

Brief introduction of 1,5-Diphenylpenta-1,4-dien-3-one

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Electric Literature of 538-58-9, Chemical Research Letters, May 2021. The prevalence of solvent effects in heterogeneous catalysis in condensed media has motivated developing quantitative kinetic, spectroscopic. In a document type is Article, and a compound is mentioned, 538-58-9, Name is 1,5-Diphenylpenta-1,4-dien-3-one, introducing its new discovery.

Complexes of the type [{(dippe)Ni} ( 2-Calpha,Cbeta- 1,4-dien-3-one)] (dippe = 1,2-bis(diisopropylphosphino)- ethane); n= 1, 2; enone = aromatic 1,4-pentadien-3-ones) were synthesized. The “[(dippe)Ni]” moiety derived from [(dippe)Ni(-H)]2 2-coordinated to the C,C double bonds of the corresponding alpha,beta-unsaturated enone and was fully characterized using a variety of spectroscopic techniques, for instance, single-crystal X-ray diffraction, nuclear magnetic resonance (NMR), and mass spectrometry. The complexes were assessed in a catalytic transfer hydrogenation process using methanol (CH3OH) as a hydrogen donor. This alcohol turned out to be a very efficient reducing and alkylating agent of 1,4- pentadien-3-ones, under neat conditions. The current methodology allowed the selective reduction of C=C bonds in alpha,beta- unsaturated enones to yield enones and saturated ketones by a homogeneous catalytic pathway, whereas by a heterogeneous pathway, the process leads to the formation of mono- and dimethylated ketones. In the latter case, the occurrence of nickel nanoparticles in the reaction media was found to participate in the catalytic alkylation of such dienones.

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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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Our interest on engineering non-ribosomal synthetase responsible for SW-163 biosynthesis prompted us to determine the relative and absolute configuration of antitumor cyclic depsipeptide SW-163s. We first isolated and identified SW-163 homologs D, F and G as known compounds UK-63598, UK-65662 and UK-63052, respectively. Both enantiomers of the unusual constitutive amino acid, N-methylnorcoromic acid, were synthesized in chiral forms starting from (R)- and (S)-1,2-propanediol. The hydrolyzate of SW-163D, a major constituent of this family, was converted with Marfey’s reagent, 1-fluoro-2,4-dinitrophenyl-5-L- alanine-amide (L-FDAA), and the resulting mixture of amino acid derivatives was subjected to an LC/MS analysis. Compared with authentic samples, the analytical data unambiguously show that SW-163D consisted of L-Ala, D-Ser and (1S, 2S)-N-methylnorcoronamic acid. The remaining stereochemistry of the N-methylcysteine moieties was determined from NOE 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