Chiral Sulfonated Phosphines. Syntheses and Use as Ligands in Asymmetric Hydrogenation Using an Aqueous-Organic Two-Phase Solvent System

Youssef Amrani, Loïc Lecomte, Denis Sinou, Jozsef Bakos, Imre Toth, Balint Heil

Research output: Contribution to journalArticle

164 Citations (Scopus)

Abstract

Sulfonation of chiral phosphines (S,S)-cyclobutanediop (1), (S,S)-BDPP (3), (S,S)-Chiraphos (5), and (R)-Prophos (7) results in water-soluble ligands. The course of the reaction has been studied by using 31P{1H} NMR. While the proper choice of the conditions permits the synthesis of tetrasulfonated cyclobutanediop 2d, BDPP 4d, and Chiraphos 6d, Prophos 7 gives a mixture of tetrasulfonated 8d and trisulfonated phosphine 8c. Treatment of [Rh(diene)Cl]2 with these novel ligands (L) results in chloride bridge splitting to give [Rh(diene)L]+ (9), which in turn reacts with hydrogen or water to give [Rh(L)(H2O)2]+ (10). Addition of (Z)-enamide, PhCH═CH(NHCOCH3)COOH (13a), to the aqua complex in water produces a substrate chelate complex 12. Rhodium(I) catalysts formed with sulfonated diphosphines are efficient catalysts for the asymmetric hydrogenation of carbon-carbon (88% ee), carbon-oxygen (28% ee), and carbon-nitrogen double bonds (58% ee) in aqueous-organic two-phase solvent systems. Sulfonated ligands afford a catalyst system, which can be reused without loss of enantioselectivity.

Original languageEnglish
Pages (from-to)542-547
Number of pages6
JournalOrganometallics
Volume8
Issue number2
DOIs
Publication statusPublished - Feb 1989

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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