Stereochemistry at carbon upon protonolysis of a late transition metal-alkyl bond: A reaction of relevance to catalytic enantioselective hydrogenation of olefins

J. A. Wiles, S. H. Bergens, Jr Young

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4 Scopus citations

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 α-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 β-olefinic carbon and transfer of ruthenium to the α-carbon in both diastereomers of 3. The two diastereomers of 3 differ by the absolute configuration at the α-carbon of MAA(H) ((S)-3 and (R)-3). The absolute configuration of the major ((S)-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 α-acetamidocinnamate (MAC) analog ([Ru((R)-BINAP)(MeCN)((S)-MAC(H))](BF4)((S)-4)) by addition of 2 equiv HBF4·Et2O in CH2 Cl2 at room temperature was not stereospecific and did not occur with β-hydride elimination from the methyl or benzyl groups.

Original languageEnglish (US)
Pages (from-to)1019-1025
Number of pages7
JournalCanadian Journal of Chemistry
Volume79
Issue number5-6
DOIs
StatePublished - Jan 1 2001

Keywords

  • BINAP
  • Catalysis
  • Enantioselective
  • Hydrogenation
  • Ruthenium

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