Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
1999-06-11
2001-02-06
Killos, Paul J. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C562S490000
Reexamination Certificate
active
06184413
ABSTRACT:
TECHNICAL FIELD
The present invention is directed to supported phase catalyst systems in which an organometallic catalyst is solubilized in the supported phase, and the use of such catalysts in asymmetric hydrogenation reactions.
BACKGROUND OF THE INVENTION
The development of effective asymmetric reactions that enable the enantioselective formation of one chiral center over another continues to be an important area of research. One such asymmetric reaction involves the introduction of a chiral center into a molecule through the enantioselective hydrogenation of a prochiral unsaturated bond by using a transition metal catalyst bearing chiral organic ligands. Numerous chiral phosphine catalysts have been developed to enantioselectively introduce chiral centers to prochiral olefins, carbonyls and imines with high enantiomeric excess. One such class of chiral catalysts employs the chiral phosphine ligand 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (hereinafter referred to as “BINAP”).
A second important area of research relates to the development of water-soluble organometallic catalysts. Conventionally, catalytically active organometallic complexes have been applied as homogeneous catalysts in solution in the organic reaction phase. Difficulties associated with recovery of the homogeneous catalysts from the reactants and products diminish the utility of these homogeneous catalysts, especially when the cost of the catalyst is high or where there is the need to isolate the reaction products in high purity.
One mode in which water soluble organometallic catalysts have been used is in two phase systems comprising an aqueous phase and a water immiscible phase (e.g. ethyl acetate-water). Separation of the organometallic catalyst from organic reactants and products is greatly simplified due to the insolubility of the catalyst in the water immiscible phase. However, in some instances, the utility of the two phase system has been limited by a lack of substrate and/or reactant solubility in the aqueous phase, by the limited interfacial area between the two phases, and by poor selectivity.
Supported phase (SP) organometallic catalysts have been developed to overcome some of the shortcomings associated with two phase reaction systems. In a supported phase system the interfacial area between the support phase, which contains the organometallic catalyst, and the water immiscible (bulk organic) phase, is greatly enhanced.
The advantages of supported phase organometallic catalyst systems have prompted further investigation into catalyst systems which will retain the beneficial characteristics thereof while further increasing yield and enantioselectivity.
SUMMARY OF THE INVENTION
Such further advantages are achieved by the present invention, which relates to supported phase catalysts in which the support phase contains a highly polar and non-aqueous liquid, such as an alcohol with two or more hydroxy groups, preferably glycerol, a triol.
In this regard, the present invention is a supported phase catalyst system wherein glycerol forms the supported phase. An organometallic compound, preferably a metal complex of chiral sulfonated 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl is dissolved in glycerol. While the use of a diol, such as ethylene glycol is within the scope of the invention, the use of glycerol in the solvent support phase in a supported phase catalyst system offers the further advantage of safety due to the relatively low toxicity of glycerol as compared to ethylene glycol.
The invention further includes the use of such supported phase catalysts for asymmetric synthesis of optically active compounds containing chiral carbon-carbon and carbon-hetero atom bonds, such as the preparation of dehydronaproxen, or the asymmetric hydrogenation of ketones, imines, or beta-keto esters, such as ethyl butyrylacetate. Generally, such asymmetric reactions include those reactions in which organometallic catalysts are commonly used, such as reduction and isomerization reactions on unsaturated substrates and carbon-carbon bond forming reactions, and specifically hydrogenation, hydroboration, hydrosilylation, hydride reduction, hydroformylation, alkylation, allylic alkylation, arylation, alkenylation, epoxidation, hydrocyanation, disilylation, cyclization and isomerization reactions.
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Davis Mark E.
Wan Kam To
California Institute of Technology
Killos Paul J.
Limbach & Limbach LLP
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