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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 783-788 
    ISSN: 1434-1948
    Keywords: Enantioselective hydrosilylation ; Oxazoline ligands ; Charge-transfer ; 4,4-Bipyridine derivatives ; 2,5-Dimethoxyacetophenone ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel N′-methylated 2-(oxazolin-2-yl)-4,4′-bipyridinium salts, bearing a chiral oxazoline moiety, were tested in the Rh(I)-catalysed enantioselective hydrosilylation. After coordination to rhodium these electron-attracting ligands are supposed to exhibit charge-transfer effects with electron-donating substrates. Therefore, a new catalytic hydrosilylation reaction with 2,5-dimethoxyacetophenone as an electron-rich substrate was developed. The results were compared with those of the non-methylated 2-(oxazolin-2-yl)-4,4′-bipyridine and related ligands. In addition, the new ligands and Rh(I)-complexes were tested in the hydrosilylation of acetophenone.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 771-781 
    ISSN: 1434-1948
    Keywords: Oxazolines ; Charge-transfer ; 4,4′-Bipyridine ; Enantioselective hydrosilylation ; Rh(I)-complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Novel 2-(4,4′-bipyridin-2-yl)oxazolines, bearing a chiral oxazoline moiety, were synthesised starting from 4,4′-bipyridine and selectively monomethylated in the N′-position. After coordination to rhodium these electron-poor ligands are supposed to exhibit charge-transfer effects with electron-donating substrates in the Rh(I)-catalysed enantioselective hydrosilylation (see next publication). Similar effects were expected from 4,4′-bipyridine- and pyrazine-bisoxazolines after complexation with rhodium. For comparison 2-(4-phenylpyridin-2-yl)oxazoline ligands were synthesised. Rh(I)-complexes of selected ligands were prepared and characterised, including an X-ray structure analysis.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 55-62 
    ISSN: 0009-2940
    Keywords: Diastereoselective hydrogenation ; Folic acid ; Immobilized optically active rhodium(I)/diphosphane catalysts ; Leucovorin ; HPLC analysis of 5-formyltetrahydrofolic acid derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For the hydrogenation of the C=N bonds in the pyrazine ring of the vitamin folic acid (1) optically active rhodium(I)/diphosphane complexes immobilized on supports such as silica gel or Al2O3 were used. The reduction was carried out at 50 bar hydrogen pressure in an aqueous solution buffered to pH 7. Thus, 5,6,7,8-tetrahydrofolic acid (2) was obtained which contains a new asymmetric center at C-6 of the pterine system. Therefore, in combination with the (S) configuration of the natural L-glutamic acid part of the molecule two diastereomers with (6S,S) and (6R,S) configuration arise. The relatively unstable tetrahydrofolic acid (2) was converted into its 5-formyl derivative folinic acid (4) by treatment with methyl formate/formic acid in a 5:1 mixture of DMSO/pyridine. The Ca salt of folinic acid (4) is the widely used drug leucovorin. The diastereomers were separated by silica gel HPLC. To the column bovine serum albumine (BSA) is covalently bound. With optically active rhodium(I)/diphosphane catalysts, immobilized on silica gel supports, a diastereoselectivity of up to 90% could be achieved in the hydrogenation of folic acid (1).
    Additional Material: 1 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 2085-2093 
    ISSN: 0009-2940
    Keywords: Diastereoselective hydrogenation ; Immobilized enantioselective rhodium(I)-diphosphane catalysts ; Folic acid ; (6S,S)-Folinic acid ; 5,6,7,8-Tetrahydrofolic acid ; N-5-(menthyloxycarbonyl)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Asymmetric Catalysis, 67[1]. - Diastereoselective Hydrogenation of Folic Acid with Optically Active Rhodium(I)-Diphosphane ComplexesWith immobilized rhodium(I)-diphosphane catalysts supported on silica gel, the C = N bonds of the pyrazine ring of folic acid (1) are reduced with hydrogen in aqueous solution to give 5,6,7,8-tetrahydrofolic acid. A mixture of the two diastereomers 2a and 3a is obtained with (6S)- and (6R)-configuration, respectively, at the newly formed asymmetric center in the pterine system and (S)-configuration in the L-glutamic acid moiety. The unstable hydrogenation products are derivatized with (-)-menthyl chloroformate. An improved HPLC procedure for the analysis of the products has been developed. By using optically active chelate phosphanes as cocatalysts together with [Rh(cod)Cl]2, a diastereomeric excess of up to 24% of the natural isomer 2a with (6S,S)-configuration is attained in the heterogeneous hydrogenation of folic acid.
    Additional Material: 3 Ill.
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