1. New developments in enantioselective hydrogenation
- Author
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Rudolf Schmid, Joseph Foricher, M. Scalone, Michel Lalonde, Yvo Crameri, Emil Albin Broger, G. Schoettel, Ulrich Zutter, R. K. Müller, and Marco Cereghetti
- Subjects
chemistry.chemical_classification ,Biphenyl ,Steric effects ,Ketone ,General Chemical Engineering ,Enantioselective synthesis ,chemistry.chemical_element ,General Chemistry ,Medicinal chemistry ,Ruthenium ,chemistry.chemical_compound ,chemistry ,Diphosphines ,Lactam ,Enol ether ,Organic chemistry - Abstract
A broad variety of atropisomeric biphenyl diphosphines have been synthesized via optically active 6,6'-dimethoxybiphenyl-2,2'-diyl-bis(diphenyl phosphonates), -bis@hosphonic dichlorides), -bis(phosphonous dichlorides) and -bis@rimary diphosphines). The usefulness of diphosphine variety in enantioselective hydrogenation was demonstrated by application to sub- strates of unconventional and unprecedented type such as an a-pyridyl ketone, yketo olefins, an a-pyrone and an enol ether of a p-keto lactam. Enantioselectivities and rates in these hydrogena- tions were markedly influenced by the electronic and steric properties of the diphosphine ligands. Of particular utility were the biphenyl diphosphines with a-fury1 and 3,5-di-t-butylphenyl groups on the P atoms. A synthesis of a tetrasulfonated biphenyl diphosphine carrying the sulfonato substituents in the paru position of the P-phenyl rings has also been developed. Ruthenium cata- lysts derived from this ligand proved highly efficient for several enantioselective hydrogenations in aqueous systems.
- Published
- 1996
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