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Graphene-catalyzed transacetalization under acid-free conditions

1,2- and 1,3-Diols are readily protected as cyclic acetals and ketals through a graphene-catalyzed transacetalization process. The methodology features an atom economic procedure since quasi-stoichiometric conditions have been developed. Unlike prior systems, the graphene-catalyzed transacetalization is performed under Br¡ãnsted and Lewis acid-free conditions and without solvent. Our method has been applied to several volatile compounds that are unsuitable for complex work-up and extensive purification steps. The very unusual catalytic properties of graphene for transacetalization reactions are ascribed to molecular charge transfer between graphene and substrates.

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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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Tetrahydrofuran antifungals

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 polyetyher ester groups (e.g., a polyether ester convertible in vivo into a hydroxy group) 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£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 Expression Rate and Enantioselectivity of an Epoxide Hydrolase by Using Directed Evolution

We describe here a strategy to improve the expression efficiency and enantioselectivity of Aspergillus niger epoxide hydrolase (ANEH) by directed evolution. Based on a blue-colony screening system using the LacZalpha (beta-galactosidase alpha peptide) complementation solubility reporter, several ANEH variants out of 15000 transformants from a random-mutagenesis library were identified that show improved recombinant expression in E. coli. Among them, Pro221Ser was subsequently used as a template for iterative saturation mutagenesis (ISM) at sites around the ANEH binding pocket. Following four rounds of ISM, a highly enantioselective mutant was identified that catalyzes the hydrolytic kinetic resolution of racemic glycidyl phenyl ether with a selectivity factor of E=160 in favor of the (S)-diol compared to WT ANEH characterized by E=4.6. Expression of this mutant is 50 times higher than that of WT ANEH. It also serves as an excellent stereoselective catalyst in the hydrolytic kinetic resolution and desymmetrization of several other structurally diverse epoxides. Copyright

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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 mono-acylation of 1,2- and 1,3-diols using (alpha,alpha- difluoroalkyl)amines

In the reaction of N,N-diethyl-alpha,alpha-difluorobenzylamine (DFBA) with 1,2- or 1,3-diols, selective mono-benzoylation occurs to afford mono-esters of the diols in good yield. The reaction is completed under mild conditions in a short reaction time. Further, prim-, sec-, and tert-diols and catechol can be converted to the corresponding mono-benzoates. DFBA is used for the protection of the hydroxy group in sugars. The selective mono-nicotinylation, formylation and pivaloylation of diols are also performed by using the corresponding difluoroalkylamines.

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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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Antioxidative response in leaves and allelochemical changes in root exudates of Ricinus communis under Cu, Zn, and Cd stress

We have previously reported that Ricinus communis is a good candidate for the phytoremediation of Cd- and Zn-contaminated soil and for fuel production. In this study, changes in the activity of antioxidant enzymes (superoxide dismutase, SOD; catalase, CAT; and guaiacol peroxidase, POD) and the contents of chlorophyll and malondialdehyde (MDA) in R. communis leaves under Cu, Zn, and Cd stress were examined. Compounds from the exudate of R. communis roots were collected and analyzed using GC-MS chromatograms. The results of enzyme activity showed that Cd treatment significantly increased the SOD content of R. communis leaves and slightly elevated the CAT content, whereas the POD content increased markedly at low Cd treatment concentrations and decreased as Cd concentrations increased. Zn treatment distinctly elevated SOD and POD content in R. communis leaves but had no great influence on CAT content. Cu treatment slightly increased CAT activity, while Cu did not evidently change SOD and POD activity. We found 17, 29, 18, 18, and 33 different compounds in the R. communis root exudates from the control group and Cd, Cu, Zn, and Cd+Cu+Zn treatment groups, respectively. The root exudates mainly included ester, alcohol, ether, amide, acid, phenol, alkanes, ketone, aromatic hydrocarbon, and nitrile compounds. However, the root exudates of R. communis grown in uncontaminated soils were dominated by esters, alcohols, and ethers. Single Cu or Zn treatment slightly changed the root exudates, which were dominated by esters, alcohols, and amides. In the Cd and Cd+Cu+Zn treatment groups, the compositions of root exudates apparently increased, with alkanes as the major species (> 88%).

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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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Boronic compounds

This invention relates to a diboron derivative of formula (I) or a diboron derivative of formula (II) or a diboron derivative of formula (III) where R1, R2, R3 and R4 are each independently selected from the group consisting of optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, a group of the formula ?(R5Q)mR6 where Q is selected from O, S, NR7, optionally substituted arylene and optionally substituted cycloalkylene, m is an integer selected from 1 to 3, the or and each R5 is independently an optionally substituted C1-C3 alkylene, R6 is C1-C3 alkyl or hydrogen, and R7 is hydrogen or C1-C12 alkyl; each X is independently selected from O, S(O)n and NR7, where n is an integer from 0 to 3, R7 is hydrogen or C1-C12 alkyl, or one or more of ?NR1R7, ?NR2R7, ?NR3R7 and ?NR4R7 represent an optionally substituted 5 or 6 membered heterocyclyl group,and A, A1 and A2 are divalent groups which may or may not be different.

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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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A New Chiral Rhodium(I) Complex of (2R,3R)-2,3-Bis(diphenylphosphino)butane for Asymmetric Hydrogenations

Rhodium(I) complexes of the new chiral ligand (2R,3R)-2,3-bis(diphenylphosphino)butane (4) – which is easily prepared from natural tartaric acid – hydrogenate alpha-(acylamino)acrylic acids to natural (S)-acylamino acids in high chemical (95-100percent) and optical (80-100percent) yields.

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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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SYNTHESIS OF BORONIC ESTER AND ACID COMPOUNDS

The invention relates to the synthesis of boronic ester and acid compounds. More particularly, the invention provides improved synthetic processes for the large-scale production of boronic ester and acid compounds, including the peptide boronic acid proteasome inhibitor bortezomib.

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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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Synthesis and Absolute Configuration of Natural 2-Pyrones

2-Pyrones are frequently produced by microorganisms and often exhibit interesting bioactivities. Therefore, a short and easy synthetic access to these natural products is desirable. Synthetic routes to nectriapyrone, gibepyrone A, racemic gulypyrone A, (+)-germicidin C, (ent)-desoxygermicidin C and (ent)-prolipyrone A via a modular approach are presented, allowing the assignment of the absolute configurations of the latter three chiral compounds. The method failed for the synthesis of (ent)-phomapyrone B that was thus synthesized via a different route, resulting in an assignment of the absolute configuration of natural phomapyrone B.

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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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Regio-, Diastereo-, and Enantioselective Synthesis of vic-Diols via alpha-Silyl Ketones According to the SAMP/RAMP Hydrazone Method

alpha-Silylated ketones 5 or 10 of high enantiomeric purity (ee>=90percent) are easily available by silylation or silylation/alkylation of ketones 1 or 6, resp., according to the SAMP/RAMP hydrazone method.Reduction of 5 or 10 with L-selectride<*>, followed by oxidative cleavage of the C-Si bond, leads to vic-diols 11-13 with high diastereoselectivity (de>=90percent) and without racemization.The stereoselectivity of the reduction depends on the structure of the alpha-silyl ketones 5 or 10, the reducing reagents, and the solvents used.Key Words: Ketones, alpha-silyl / vic-Diols, diastereo- and enantioselective synthesis / SAMP/RAMP Hydrazones / L-Selectride reductions

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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