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Dimethyl (3R,4R)- and (3S,4S)-diphenyladipate were synthesized enantioselectively by electroreductive intermolecular hydrocoupling of chiral N-trans-cinnamoyl-2-oxazolidones and subsequent methanolysis.

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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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Compounds structurally related to 2-cyclohexen-1-one 1,4-di-O-benzyl-L-threitol ketal were prepared and subjected to the Simmons-Smith cyclopropanation.From these experiments a mechanistic model for diastereoselective cyclopropanation of common ring systems (five-, six-, and seven-membered) has been formulated.Diastereoselectivity is thought to result from preferential chelation of the Simmons-Smith reagent at the least sterically hindered lone pair of electrons on the dioxolane oxygen proximal to the alkene.It is found that the presence of oxygen atoms in the dioxolane appendages provide sites for competitive chelation of the reagent, which can antagonize the diastereoselection due to chelation at dioxolane oxygen.That chelation by dioxolane oxygen does occur and is responsible for diastereoselectivity is inferred from studies with a hydrocarbon model system.Surprisingly, both dioxolane appendages are shown to be necessary for optimum diastereoselection since, under the conditions of the Simmons-Smith cyclopropanation, 2-cycloalken-1-one ethylene ketals are reversibly ring opened to zwitterionic intermediates.

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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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Compounds structurally related to 2-cyclohexen-1-one 1,4-di-O-benzyl-L-threitol ketal were prepared and subjected to the Simmons-Smith cyclopropanation.From these experiments a mechanistic model for diastereoselective cyclopropanation of common ring systems (five-, six-, and seven-membered) has been formulated.Diastereoselectivity is thought to result from preferential chelation of the Simmons-Smith reagent at the least sterically hindered lone pair of electrons on the dioxolane oxygen proximal to the alkene.It is found that the presence of oxygen atoms in the dioxolane appendages provide sites for competitive chelation of the reagent, which can antagonize the diastereoselection due to chelation at dioxolane oxygen.That chelation by dioxolane oxygen does occur and is responsible for diastereoselectivity is inferred from studies with a hydrocarbon model system.Surprisingly, both dioxolane appendages are shown to be necessary for optimum diastereoselection since, under the conditions of the Simmons-Smith cyclopropanation, 2-cycloalken-1-one ethylene ketals are reversibly ring opened to zwitterionic intermediates.

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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 detailed procedure for the synthesis of Ru-SYNPHOS and Ru-DIFLUORPHOS catalysts are described. These catalysts displayed high rates and are quite effective for the large-scale hydrogenation reactions of unsaturated compounds. Georg Thieme Verlag Stuttgart.

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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 C2 amidine derivative (S,S)-1, as a twisted chiral dual acceptor for hydrogen bonding, was designed and synthesized. Enantioselective binding between (S,S)-1 and a series of diol enantiomers was investigated by NMR spectroscopy. High enantioselection above 1.0 kcal/mol was achieved in CDCl3. The association mode based on dual N···HO interactions was confirmed by intermolecular NOEs.

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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 alpha-hydroxy ketones are used as building blocks for compounds of pharmaceutical interest (such as antidepressants, HIV-protease inhibitors and antitumorals). They can be obtained by the action of enzymes or whole cells on selected substrates, such as diketones. We have studied the enantiospecificities of several fungal (AKR3C1, AKR5F and AKR5G) and human (AKR1B1 and AKR1B10) aldo-keto reductases in the production of alpha-hydroxy ketones and diols from vicinal diketones. The reactions have been carried out with pure enzymes and with an NADPH-regenerating system consisting of glucose-6-phosphate and glucose-6-phosphate dehydrogenase. To ascertain the regio and stereoselectivity of the reduction reactions catalyzed by the AKRs, we have separated and characterized the reaction products by means of a gas chromatograph equipped with a chiral column and coupled to a mass spectrometer as a detector. According to the regioselectivity and stereoselectivity, the AKRs studied can be divided in two groups: one of them showed preference for the reduction of the proximal keto group, resulting in the S-enantiomer of the corresponding alpha-hydroxy ketones. The other group favored the reduction of the distal keto group and yielded the corresponding R-enantiomer. Three of the AKRs used (AKR1B1, AKR1B10 and AKR3C1) could produce 2,3-butanediol from acetoin. We have explored the structure/function relationships in the reactivity between several yeast and human AKRs and various diketones and acetoin. In addition, we have demonstrated the utility of these AKRs in the synthesis of selected alpha-hydroxy ketones and diols.

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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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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:
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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6-Isopropenyl 3-methyl 9-decene yl acetate (3S, 6R) has been synthesized from readily available trans(-)-dihydrocarvone.Regioselective ozonolysis of this ketone silyl enol ether is the key step of the sequence and allows to preserve both chiral centers.

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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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Production of highly pure (2S,3S)-2,3-butanediol ((2S,3S)-2,3-BD) and (3S)-acetoin ((3S)-AC) in high concentrations is desirable but difficult to achieve. In the present study, glucose was first transformed to a mixture of (2S,3S)-2,3-BD and meso-2,3-BD by resting cells of Klebsiella pneumoniae CICC 10011, followed by biocatalytic resolution of the mixture by resting cells of Bacillus subtilis 168. meso-2,3-BD was transformed to (3S)-AC, leaving (2S,3S)-2,3-BD in the reaction medium. Using this approach, 12.5gl-1 (2S,3S)-2,3-BD and 56.7gl-1 (3S)-AC were produced. Stereoisomeric purity of (2S,3S)-2,3-BD and enantiomeric excess of (3S)-AC was 96.9 and 96.2%, respectively.

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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