Asymmetric hydrogenation of enamides with Rh-BisP* and Rh-MiniPHOs catalysts. Scope, limitations, and mechanism

I. D. Gridnev, M. Yasutake, N. Higashi, T. Imamoto

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166 Citations (Scopus)

Abstract

The asymmetric hydrogenation of aryl- and alkyl-substituted enamides catalyzed by Rh-BisP* complex affords optically active amides with very high ee values. The Rh-MiniPHOS catalyst gives somewhat less satisfactory results. Hydrogenation of the aryl-substituted enamides with (S,S)-BisP*-Rh catalyst gives R-amides, whereas the t-Bu- and 1-adamantyl-substituted enamides give S-products with 99% ee. Reaction of [Rh(BisP*)(CD3OD)2]BF4 (11) with CH2=C(C6H5)NHCOCH3 (5) gives two diastereomers of the catalyst-substrate complex (12a,b), which interconvert reversibly by both intra- and intermolecular pathways as shown by EXSY data. Only one isomer in equilibrium with solvate complex 11 was detected for each of the catalyst-substrate complexes 17 and 18 obtained from CH2=C(t-Bu)NHCOCH3 (6) or CH2=C(1-adamantyl)NHCOCH3 (7). Hydrogenation of these equilibrium mixtures at -100 °C gave monohydride intermediates 19 and 20, respectively. In these monohydrides the Rh atom is bound to the β-carbon. A new effect of the significant decrease of ee was found for the asymmetric hydrogenation of CH2=C(C6H4OCH3-o) NHCOCH3 (21), when H2 was substituted for HD or D2.

Original languageEnglish
Pages (from-to)5268-5276
Number of pages9
JournalJournal of the American Chemical Society
Volume123
Issue number22
DOIs
Publication statusPublished - 2001 Oct 10
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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