Asymmetric Hydrogenation Catalyzed by (S,S)-R-BisP*-Rh and (R,R)-R-MiniPHOS Complexes: Scope, Limitations, and Mechanism

Ilya D. Gridnev, Yoshinori Yamanoi, Natsuka Higashi, Hideyuki Tsuruta, Masaya Yasutake, Tsuneo Imamoto

Research output: Contribution to journalArticle

148 Citations (Scopus)

Abstract

A new class of chiral C2-symmetric bis(trialkyl)phosphine ligands has been prepared and used in Rh(I)-catalyzed asymmetric hydrogenation reactions. The ligands, 1,2-bis(alkylmethylphosphino)ethanes 1 a-g (abbreviated as BisP*, alkyl = t-butyl, 1-adamantyl, 1-methylcyclohexyl, 1,1-diethylpropyl, cyclopentyl, cyclohexyl, isopropyl) and 1,2-bis(alkylmethylphosphino)methanes 2 a-d (abbreviated as MiniPHOS, alkyl = t-butyl, cyclohexyl, isopropyl, phenyl) are prepared by a simple synthetic approach based on the air-stable phosphine-boranes. These new ligands give the corresponding Rh(I) complexes, which are effective catalytic precursors for the asymmetric hydrogenation of a representative series of dehydroamino acids and itaconic acid derivatives. Enantioselectivities observed in these hydrogenations are universally high and in many cases exceed 99%. X-Ray characterization of four precatalysts, study of the pressure effects, deuteration experiments, and characterization of the wide series of intermediates in the catalytic cycle are used for the discussion of the possible correlation between the structure of the catalysts and the outcome of the catalytic asymmetric hydrogenation.

Original languageEnglish
Pages (from-to)118-136
Number of pages19
JournalAdvanced Synthesis and Catalysis
Volume343
Issue number1
Publication statusPublished - 2001 Jan
Externally publishedYes

Keywords

  • Amino acids
  • Asymmetric catalysis
  • Homogeneous catalysis
  • Hydrogenations
  • P ligands
  • Rhodium

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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