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Homogeneous Catalysis with Metal Phosphine Complexes pp 137–165Cite as

Asymmetric Hydrogenation Reactions Using Chiral Diphosphine Complexes of Rhodium

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Part of the book series: Modern Inorganic Chemistry ((MICR))

Abstract

The archetypal reaction in asymmetric homogeneous hydrogenation is reduction of a z-acyldehydroamino acid to the corresponding amino acid derivative, which represents one of the most efficient routes to introduction of a chiral center, with optical yields often in excess of 98 0/0. Soon after Wilkinson's discovery that tris(triphenylphosphine)rhodium chloride was a homogeneous catalyst for alkene hydrogenation,'!' several authors realized the potential for asymmetric induction. Early attempts using simple resolved chiral phosphines were not impressive,(2) and the first major development was due to Kagan and Dang.(3) They demonstrated that the use of a chiral chelating biphosphine, (1) (see Figure 4.1), bearing the now-famous acronym of DIOP, gave good optical yields, particularly in the reduction of dehydroamino acid derivatives. The most startling aspect of

Some of the commoner biphosphines which have been successfully employed in asymmetric catalysis.

this result is that the chiral center in the catalyst which controls asymmetric induction is three bonds removed from the metal and spatially remote from it. This leads to an immediate suspicion that the chelate ring is in some way controlling the orientation of the P-Ph rings, which in turn determines the stereochemical outcome of the rate-determining stage in catalysis. A second development, one of considerable commercial significance, was due to W. S. Knowles and co-workers at Monsanto.

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Authors and Affiliations

  1. Dyson Perrins Laboratory, South Parks Road, Oxford, OX1 3QY, England

    Dr. John M. Brown

  2. School of Molecular Sciences, University of Sussex, Falmer, Brighton, UK

    Dr. Penny A. Chaloner

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  1. Dr. John M. Brown
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  2. Dr. Penny A. Chaloner
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  1. University of Minnesota, Minneapolis, Minnesota, USA

    Louis H. Pignolet

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Brown, J.M., Chaloner, P.A. (1983). Asymmetric Hydrogenation Reactions Using Chiral Diphosphine Complexes of Rhodium. In: Pignolet, L.H. (eds) Homogeneous Catalysis with Metal Phosphine Complexes. Modern Inorganic Chemistry. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-3623-5_4

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