ジホスフィンロジウムおよびルテニウム錯体を用いるデヒドロアミノ酸類の触媒的不斉水素化の機構研究の新展開  [in Japanese] Recent Advances of Mechanistic Studies on Asymmetric Hydrogenation of Dehydroamino Acid Derivatives Catalyzed by Diphosphine-Rh and -Ru Complexes  [in Japanese]

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Author(s)

Abstract

The Rh-catalyzed enantioselective hydrogenation of <I>N</I>-acylated dehydroamino acids or their esters, initiated by Kagan, constitutes now a standard tool for the synthesis of natural and unnatural amino acids of high enantiomeric purity. The reaction proceeds via the unsaturate-dihydride mechanism in which the oxidative addition of hydrogen to Rh-enamide complex is the rate-limiting and stereodifferentiating step. In addition to this standard pathway, alternative dihydrideunsaturate mechanisms have also been reported. The formation of a RhH<SUB>2</SUB> may precede the olefin-Rh interaction, depending on the chiral ligands and reaction conditions. Reactions using BINAP-Ru (II) complexes (BINAP = 2, 2'-bis (diphenylphosphino) -1, 1'-binaphthyl), find a wider synthetic scope, allowing asymmetric hydrogenation of a range of functionalized olefins and ketones. Interestingly, the Rh and Ru complexes with the same BINAP ligand exhibit an opposite sense of asymmetric induction in hydrogenation of dehydroamino acid derivatives. This review summarizes some mechanistic studies in this hydrogenation catalyzed by diphosphine-Rh and-Ru complexes.

Journal

  • Journal of Synthetic Organic Chemistry, Japan

    Journal of Synthetic Organic Chemistry, Japan 63(9), 899-910, 2005

    The Society of Synthetic Organic Chemistry, Japan

Codes

  • NII Article ID (NAID)
    130000928548
  • NII NACSIS-CAT ID (NCID)
    AN0024521X
  • Text Lang
    JPN
  • ISSN
    0037-9980
  • NDL Article ID
    7477568
  • NDL Source Classification
    ZP11(科学技術--化学・化学工業--有機化学・有機化学工業)
  • NDL Call No.
    Z17-256
  • Data Source
    NDL  J-STAGE 
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