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Mechanistic Studies of Diastereoselective Cyclopropanation via Homochiral Ketals. 2. Studies with Conformationally Restricted 2-Cyclohexen-1-one Ketals

The effect of cyclohexene ring conformation on the diastereoselectivity observed for Simmons-Smith cyclopropanation of 2-cyclohexen-1-one ethylene ketals was examined by using (5S)-5-tert-butyl-2-cyclohexen-1-one 1,2-ethanediol, (2R,3R)-2,3-butanediol, and (2S,3S)-2,3-butanediol ketals.Reagent chelation by the pseudoequatorial dioxolane oxygen atom was shown to result in more effective methylene transfer.This regiochemical preference can either antagonize or reinforce diastereoselectivity due to steric hindrance of the dioxolane oxygen atoms from dissymmetric placement of methyl appendages on the dioxolane ring.

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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 simple and highly efficient procedure for construction of quaternary carbons centers by tributylphosphine catalyzed bis-Michael addition

The tributylphosphine-catalyzed bis-Michael addition reaction of various kinds of alpha,beta-unsaturated carbonyl compounds with active methylenes is described. This is a convenient and rapid method for generating quaternary carbons centers and useful procedure for the synthesis of branched core and highly substituted trans cyclohexanones. All the reactions were completed in 60 min and afford the corresponding products in excellent 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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An antibody-catalyzed isomerization reaction

Monoclonal antibodies (mAbs) were generated against the coplanar transition state (TS(paragraph)) analogue 1 and assayed for their ability to catalyze the isomerization of bridged biphenyls 4, 6, and 7. This is a relatively simple unimolecular reaction whose activation barrier arises from unfavorable steric interactions between the two benzylic methylene groups and strain in the bridging ring system. Seven mAbs were found that catalyzed the isomerization of 4 to 6; the most efficient (mAb 64D8E10) has k(cat) and K(M) values of 4.3 x 10-5 s-1 and 420 muM, respectively. This corresponds to a rate enhancement over the unimolecular uncatalyzed reaction (k(cat)/k(uncat)) of 2900. The dissociation constant for the TS(paragraph) analogue, K(d), was determined to be 210 nM. For both the antibody (64D8E10) catalyzed and uncatalyzed reactions, the free energy of activation (DeltaG(paragraph)) is comprised largely of the enthalpy term; the antibody decreases the enthalpy of activation by 5 kcal/mol. Despite relatively large differences in the values of k(cat)/k(uncat) for the five antibodies, the ratios of K(d) to K(M)(4) are very similar. It is likely that the antibodies catalyze this reaction by reducing both ring strain and nonbonded steric interactions in the transition state.

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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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AlEt3-promoted eliminative ring-opening of beta-hydroxy epoxides: Highly stereoselective synthesis of terminal alpha-hydroxy olefins

AlEt3-promoted eliminative ring-opening of beta-epoxy alcohols leading to alpha-hydroxy olefins is reported. This eliminative ring-opening reaction is shown to be highly stereoselective, thus providing an alternative asymmetric synthesis for alpha-hydroxy olefins.

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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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Unexpected bond activations promoted by palladium nanoparticles

Thioether-phosphines, 1 and 2, were applied for the stabilisation of palladium nanoparticles (PdNPs) synthesised by a bottom-up methodology, using [Pd2(dba)3] as an organometallic precursor. For the phenyl containing ligand 1, small (dmean = 1.6 nm), well-defined and dispersed nanoparticles were obtained; however, ligand 2 involving a long alkyl chain led to agglomerates. NMR and GC-MS analyses throughout the synthesis of the nanomaterials revealed partial cleavage of ligands by C-S and C-P bond activations, and XPS spectra of the isolated nanoparticles indicated the presence of both thioether-phosphines and their fragments on the metallic surface. Reactivity studies of molecular palladium systems as well as on extended palladium surfaces pointed out that cluster entities are responsible for C-heteroatom activations, triggering structure modifications of stabilisers during the synthesis of PdNPs. the Partner Organisations 2014.

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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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Functionalized naphthalenes by benzotriazole-mediated annulation

The anions of 3-benzotriazolylphthalide (1) and of 2- (benzotriazolylmethyl)benzonitrile (6) condense regioselectively with a range of Michael acceptors to form 1,4-dihydroxynaphthalenes 4b-f and 1-amino-2,3- di(methoxycarbonyl)naphthalene (9) in moderate to good 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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PROCESS FOR THE PREPARATION OF DAPAGLIFLOZIN

The present invention discloses a novel process for the preparation of Dapagliflozin (S)-propylene glycol hydrate of Formula II. (Formula II)

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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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In heterogeneous catalysis, the catalyst is in a different phase from the reactants. Application In Synthesis of (2S,3S)-Butane-2,3-diol, At least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way. 19132-06-0, name is (2S,3S)-Butane-2,3-diol. In an article£¬Which mentioned a new discovery about 19132-06-0

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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Induction of a preferred twist in a biphenyl core by stereogenic centers: A novel approach to the absolute configuration of 1,2- and 1,3-diols

A quick, simple, and reliable method to assign the absolute configuration of 1,2- and 1,3-diols: all that is needed is to measure the CD sign of the A band (250 nm) of their biphenyldioxolanes 1 (n = 0,1). The chirality of the diol induces a preferred sense of twist in the biphenyl moiety (R,R-M and S,S-P), and a positive A band (a probe of M twist) reveals an R or R,R configuration of the diol.

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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