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(S)-1,2-Alkanediols, which were the opposite configuration to those produced by baker’s yeast-mediated bioreduction of corresponding 1-hydroxy-2-alkanones, were prepared by baker’s yeast-mediated oxidation.Treatment of racemic 1,2-alkanediols with baker’s yeast under the aerobic condition followed by removal of the corresponding 1-hydroxy-2-alkanones, which were produced by enantioselective oxidation of (R)-1,2-alkanediols, afforded (S)-1,2-alkanediols.

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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 absolute configuration of 1,2-diols formed by a primary and a secondary (chiral) hydroxyl group can be deduced by comparison of the 1H NMR spectra of the corresponding (R)- and bis-(S)-MPA esters (MPA = methoxyphenylacetic acid). This method involves the use of the chemical shifts of substituents L1/L2 attached to the secondary (chiral) carbon, and of the hydrogen atom linked to the chiral center (Calpha-H) as diagnostic sig nais. Theoretical (AM1, HF, and B3LYP calculations) and experimental data (dynamic and low-temperature NMR spectroscopy, studies on deuterated derivatives, constant coupling analysis, circular dichroism (CD) spec tra, and NMR studies with a number of diols of known absolute configuration) prove that the signs of the DeltadeltaRS obtained for those signals correlate with the absolute configuration of the diol. A graphical model for the reliable assignment of the absolute configuration of a 1,2-diol by comparison of the NMR spectra of its bis-(R)- and bis-(S)-MPA esters is presented.

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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 family of chiral (3,3?-di-tert-butyl-5,5?,6,6?- tetramethyl-2,2?-biphenol-derived) phosphine-phosphite ligands (P-OP) with a substituted ethane backbone has been synthesized and the performance of these ligands in the Rh-catalyzed enantioselective hydrogenation and hydroformylation of several representative olefins analyzed. Corresponding cationic rhodium complexes provide highly enantioselective catalysts for the hydrogenation of methyl (Z)-alpha-acetamidocinnamate (MAC) and dimethyl itaconate. The catalyst comparison indicates that, for the two substrates, product configuration is determined by the configuration of the phosphite. Regarding matching and mismatching effects in these hydrogenations, small effects were observed in the reduction of MAC, while for the itaconate the bigger difference between the matched and mismatched cases was of 21% ee. On the other hand, Rh catalysts based on P-OP ligands showed good levels of activity and regioselectivity in the hydroformylation of styrene and allyl cyanide, while moderate enantioselectivities were obtained. Participation of the two stereogenic elements has been observed in these reactions, and their mismatched combination leads to cancellation of enantioselectivity. To further investigate the influence of the ligand backbone in the course of these reactions, structures of rhodium model complexes Rh(Cl)(CO)(P-OP) were analyzed by DFT methods. The results obtained indicate the existence of two types of preferred conformations, whose relative stability depend on the backbone nature. Comparison of structures of the more stable conformers for each ligand indicates that the orientation of the biaryl phosphite group with respect to the coordination plane does not vary substantially along the series. Differently, the position of the phenyl phosphine substituents greatly depends on the backbone. On the basis of these observations it has been concluded that chiral induction in the hydrogenation is very predominantly due to the phosphite part of the ligand. Alternatively, conformation of the phosphine group has a great influence on enantioselectivity in the hydroformylation reactions, and even reversal of product configuration was observed between catalysts with an opposite axial equatorial arrangement of Ph phosphine substituents.

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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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Cobalt complexes of fluorous chiral salen ligands have been synthesized and tested as catalysts in the hydrolytic kinetic resolution of terminal epoxides. Whereas the activity of heavily fluorinated complexes was found to be rather low, a ‘light fluorous’ complex was shown to be an efficient and highly selective catalyst for this asymmetric ring-opening reaction. Several strategies for the isolation of reaction products and the recovery of the fluorous catalyst are also discussed.

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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 activation of inactive Jacobsen’s chiral salen Co(ii) (salen = N,N?-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine) compound is attained by dinuclear chiral salen Co(iii)-OTf complex formation with yttrium triflate. The yttrium metal not only displays a promoting effect on electron transfer, but also assists in forming two stereocentres of a Lewis acid complex with Co(iii)-OTf. We found that the binuclear Co-complex significantly enhanced reactivity and enantioselectivity in the hydrolytic kinetic resolution of terminal epoxides compared to its analogous monomer and kinetic data are also consistent with these results.

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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 liquid crystal compound of the formula: STR1 wherein m and n are independently integers of 1 to 22; k and l are independently integers of 1 to 2; and C* is an asymmetric carbon atom, is chemically stable and can be applied to liquid crystal display devices operable at room temperature.

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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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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:
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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Compositions comprising stereocomplexes of enantiomeric polymer chains having individual repeat units formed from the reaction of an epoxide and cyclic anhydride. The compositions can be made by mixing two types of enantiomeric polymer chains having opposite absolute stereochemistry. The compositions can be used in applications such as biomedical applications and drug delivery applications.

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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 novel series of chiral dopants synthesized from (S)-1,2-propanediol and mesogenic carboxylic acids were characterized by FT-IR, 1H NMR, elemental analysis and their helical twisting properties were investigated by doping the chiral dopants into a nematic liquid crystal host (SLC-1717). The results show that, the helical pitch of N*-LC mixture exhibited a terminal alkyl chain length dependence and the molecular twisting power beta also exhibited a temperature dependence (increasing beta with increasing temperature).

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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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Wavelength and mass resolved resonance-enhanced multiphoton ionization (REMPI) excitation spectra of (R)-(+)- 1-phenyl-1-propanol (PR) and its complexes with some chiral diols, i.e. 1,2-propanediols. 2.3-butanediols, and 2,4-pentanediols, have been recorded after a supersonic molecular beam expansion and interpreted in the light of molecular dynamic (MD) conformational minima searches. The spectral features of the selected complexes were found to depend on cooperative hydrogen-bond interactions between the two components, whose intensity depends upon the specific configuration of the diol moiety and the relative position of its hydroxy groups. The study further confirms resonant two-photon ionization spectroscopy, coupled with time-of-flight mass resolution (R2PI-TOF), as an excellent tool for gathering valuable information on the interactive forces in molecular clusters and for enantiodiscrimination of chiral molecules in the gas phase.

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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