Enantioselective catalytic double and triple carbonylation of olefins

Conference · Sun Dec 31 04:00:00 EST 1995

OSTI ID:250108

Sperrle, M; Consiglio, G ^[1]

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1. Swiss Federal Institute of Technology, Zuerich (Switzerland)

The first enantioselective double carbonylation of olefins to succinates was realized using PdX{sub 2}(L-L) complexes (X is a weakly or non-coordinating anion, L-L a chelate phosphorus ligand) as the catalyst precursor. With [Pd(H{sub 2}O){sub 2}((S)-2,2{prime}-dimethoxy-6,6{prime}-bis(diphenyl-phosphino)biphenyl)][CF{sub 3}SO{sub 3}]{sub 2} high enantioselectivity (up to 95% ee) for styrene (R = C{sub 6}H{sub 5}) was achieved. For aliphatic olefins with the same catalytic system enantioselectivity is modest (15-30% ee). Basic ligands such as 2,2{prime}-dimethoxy-6,6{prime}-bis(dicyclohexylphosphino)-biphenyl bring about an improvement of the enantioselectivity (e.g., {approximately}70% for propene). By increasing the carbon monoxide pressure an increasing formation of other products, namely dimethyl 2-oxoglutarates is observed. This is the first observed example of a triple carbonylation of olefins. Even though the chemoselectivity is not high, this reaction allows a one step synthesis of substituted 2-oxoglutarates with fair to excellent enantioselectivity (e.e. up to 95%). The reaction is completely regioselective for styrene giving exclusive formation of dimethyl 2-oxo-3-phenylglutarate (R = C{sub 6}H{sub 5}); with aliphatic olefins two regioisomers are usually formed. For propene various diphosphine ligands have been used. The enantioselectivity is interpreted on the basis of an asymmetric induction that is mostly sterically controlled and that arises from an interplay between regioselectivity and enantioface selection during olefin insertion.

• OSTI ID: 250108
• Report Number(s): CONF-9508100--
• Country of Publication: United States
• Language: English

Related Subjects

10 SYNTHETIC FUELS
40 CHEMISTRY
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CARBONYLATION
CATALYSTS
CATALYTIC EFFECTS
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ORGANOMETALLIC COMPOUNDS
PALLADIUM COMPLEXES
STEREOCHEMISTRY