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Practical catalytic cross-coupling of secondary alkyl electrophiles with secondary alkyl nucleophiles under Cu catalysis has been realized. The use of TMEDA and LiOMe is critical for the success of the reaction. This cross-coupling reaction occurs via an SN2 mechanism with inversion of configuration and therefore provides a general approach for the stereocontrolled formation of C-C bonds between two tertiary carbons from chiral secondary alcohols.

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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 application relates to novel substituted piperidines of the general formula (I) in which R1, R2, R3, R 4, W, X, Z, m and n are each as defined in detail in the description, to a process for their preparation and to the use of these compounds as medicines, in particular as renin inhibitors.

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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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(Matrix presented) Massadine, a highly oxygenated alkaloid, was isolated from the marine sponge Stylissa aff. massa as an inhibitor of geranylgeranyltransferase type I (GGTase I). The structure of massadine has been deduced from spectral data. Massidine inhibited GGTase I from Candida albicans with an IC50 value of 3.9 muM.

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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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(Chemical Equation Presented) We have designed a series of diphosphite ligands to study the effect of the backbone, the size of the chelate ring, and the substituents of the biphenyl moieties and to determine the scope of this type of ligand in the Pd-catalyzed asymmetric substitution reactions of different types of substrates. Good-to-excellent activities and enantioselectivities have been obtained for disubstituted linear substrate 11 (TOF’s up to >2000 mol × (mol × h)-1, ee values up to 99%) and cyclic substrate 14 (TOF up to 285 mol × (mol × h) -1, ee values up to 92%). However, these ligands are inadequate for the Pd-catalyzed allylic alkylation of monosubstituted linear substrates because they provide low enantioselectivities.

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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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Stereoisomers of distinct chiral amino acids were observed to occur in L-enantioenriched form in carbonaceous chondrite meteorites. Meteoritic amines and monocarboxylic acids were recently shown to occur in racemic ratio. In this study we investigated the electronic circular dichroism and anisotropy spectra of chiral alcohols, chiral amines, and chiral monocarboxylic acids. We recorded circular dichroism and anisotropy spectra from 280 to 170 nm in aqueous solution using a synchrotron-radiation ultraviolet circular dichroism spectrophotometer. The obtained anisotropy spectra are employed to discuss the likely role of ultraviolet circularly polarized light leading to enantioenriched amino acids, as well as racemic amines and monocarboxylic acids during their primordial interstellar synthesis. These data will moreover accompany the European Space Agency’s Rosetta mission, which successfully landed Philae on the nucleus of comet 67P/Churyumov?Gerasimenko to search for chiral organic molecules.

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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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Ruthenium complexes of phosphinoferrocenylaminophosphine ligands (BoPhoz ligands) have been prepared by combining the ligands with tris(triphenylphosphine)ruthenium dichloride and precipitating the complexes. The optimal species exhibit high enantioselectivities for the asymmetric hydrogenation of functionalized ketones, particularly beta-ketoesters.

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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 title compounds 1 to 6 (Table 1) are shown by 1H, 11B, and 15N NMR shifts to form an intramolecular B-N bond which, according to 1H and 13C NMR, is frequently broken (DeltaGc* = 40 to 54 kJ/mol, Table 2) and re-formed.

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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 specification generally relates to compounds of Formula (I): and pharmaceutically acceptable salts and prodrugs thereof, where R1, R4, R5, R6, R7, Linker, X, Y, A, G, D and E have any of the meanings defined herein. This specification also relates to the use of such compounds and pharmaceutically acceptable salts and prodrugs thereof in methods of treatment of the human or animal body, for example in prevention or treatment of cancer. This specification also relates to processes and intermediate compounds involved in the preparation of such compounds and to pharmaceutical compositions containing them.

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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 hydrolytic kinetic resolution (HKR) of terminal epoxides, using chiral chromium(III)-salen catalysts based on DIANANE (endo,endo-2,5-diaminonorbornane) , was studied. A broad substrate scope was found for the chromium(III)-DIANANE catalysts, and very low loadings (down to 0.05 mol%) were needed to achieve high enantiomeric purities of both the remaining epoxides and the product diols (up to >99% ee). Besides monosubstituted epoxides, 2-methyl-2-n-pentyloxirane, which is an example for 2,2-disubstituted epoxides, could be ring-opened in an asymmetric fashion with water in the presence of an electronically tuned chromium-(III)-DIANANE complex.

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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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BACKGROUND: 2,3-Butanediol (2,3-BD) has a wide range of applications in chiral molecular synthesis, biofuel additives, and in food flavor additive manufacturing. Fermentation is a favorable method for 2,3-BD production. However, it requires much time and produces several NADH related byproducts which compete with 2,3-BD production. Bacillus subtilis has an excellent ability for 2,3-BD production by biocatalysis. However, its production is limited by low intracellular NADH and the reversible property of acetoin reductase (AR/2,3-BDH). The whole cell biocatalyst process with two different NADH regeneration systems was designed for efficient production of 2,3-BD in B. subtilis 168. RESULTS: Formate dehydrogenase and glucose dehydrogenase for NADH regeneration were successfully co-expressed with acetoin reductase in B. subtilis 168. After optimization of biocatalyst bioconversion conditions, B. subtilis 168/pMA5-bdhA-HpaII-fdh yielded 74.5 g L?1 of 2, 3-BD with 9.3 g L?1 h?1 productivity by fed batch and 115.4 g of 2,3-BD was achieved using same batch bacterium by three repeated batch bioconversions. On the other hand, 63.7 g L?1 of 2, 3-BD was produced with 7.92 g L?1 h?1 productivity by B. subtilis 168/pMA5-bdhA-HpaII-gdh. To our knowledge, the volume productivity obtained here is the highest ever reported for biocatalysis. CONCLUSION: A higher productivity of 2,3-BD from acetoin was achieved by whole cell biocatalysis with NADH regeneration systems in B. subtilis 168. This approach can be applied for NADH related bio-based chemicals production to improve titer, yield and productivity.

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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