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Titolo:
Stereochemistry at carbon upon protonolysis of a late transition metal-alkyl bond: a reaction of relevance to catalytic enantioselective hydrogenation of olefins
Autore:
Wiles, JA; Bergens, SH; Young, VG;
Indirizzi:
Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada Univ Alberta Edmonton AB Canada T6G 2G2 hem, Edmonton, AB T6G 2G2, Canada Univ Minnesota, Dept Chem, Xray Crystallog Lab, Minneapolis, MN 55455 USA Univ Minnesota Minneapolis MN USA 55455 og Lab, Minneapolis, MN 55455 USA
Titolo Testata:
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE
fascicolo: 5, volume: 79, anno: 2001,
pagine: 1019 - 1025
SICI:
0008-4042(200105)79:5<1019:SACUPO>2.0.ZU;2-4
Fonte:
ISI
Lingua:
ENG
Soggetto:
BIOLOGICALLY IMPORTANT LIGANDS; UNSATURATED CARBOXYLIC-ACIDS; ASYMMETRIC HYDROGENATION; PHOSPHINE COMPLEXES; DITERTIARY PHOSPHINE; OXIDATIVE ADDITION; DIPHOSPHINE COMPLEXES; CHELATING DIPHOSPHINE; RUTHENIUM COMPLEXES; MECHANISTIC ASPECTS;
Keywords:
ruthenium; BINAP; enantioselective; hydrogenation; catalysis;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
59
Recensione:
Indirizzi per estratti:
Indirizzo: Bergens, SH Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada Univ Alberta Edmonton AB Canada T6G 2G2 n, AB T6G 2G2, Canada
Citazione:
J.A. Wiles et al., "Stereochemistry at carbon upon protonolysis of a late transition metal-alkyl bond: a reaction of relevance to catalytic enantioselective hydrogenation of olefins", CAN J CHEM, 79(5), 2001, pp. 1019-1025

Abstract

Reaction of [Ru((R)-BINAP)(H)(MeCN)(n)(acetone)(3-n)](BF4) (where n = 0-3)(2) with 1 equiv of the olefin substrate methyl alpha-acetamidoacrylate (MAA) in acetone at room temperature immediately generated a mixture (72:28) of two diastereomers of the complex [Ru((R)-BINAP)(MeCN)(MAA(H))](BF4) (3). The olefin-hydride insertion reaction between 2 and MAA to generate 3 was regioselective, with transfer of the hydride to the beta-olefinic carbon and transfer of ruthenium to the alpha-carbon in both diastereomers of 3. Thetwo diastereomers of 3 differ by the absolute configuration at the alpha-carbon of MAA(H) ((S-C alpha)-3 and (R-C alpha)-3). The absolute configuration of the major ((S-C alpha)-3) diastereomer was determined by X-ray diffraction in conjunction with NMR spectroscopic data. Protonolysis of the ruthenium-carbon bond in 3 and in the methyl alpha-acetamidocinnamate (MAC) analog ([Ru((R)-BINAP)(MeCN)((S)- MAC(H))](BF4) ((S-C alpha)-4)) by addition of2 equiv HBF4.Et2O in CH2Cl2 at room temperature was not stereospecific anddid not occur with beta-hydride elimination from the methyl or benzyl groups.

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Documento generato il 16/07/20 alle ore 19:53:51