Enantioselectivity in the catalytic hydroesterification of acenaphthylene: direct evidence of the racemization of PdII-alkyl species by a degenerate substitution equilibrium with Pd0Ln

Literature Information

Publication Date 2003-06-13
DOI 10.1039/B304553F
Impact Factor 6.222
Authors

Jordi Gironès, Josep Duran, Alfonso Polo, Julio Real


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Abstract

The palladium catalyzed hydroesterification of acenaphthylene takes place through a “hydride” mechanism, that is, through the selective cis insertion of the olefin into the palladium–hydride bond, an obvious prerequisite for the successful development of an enantioselective version of the reaction; however, a degenerate substitution equilibrium between Pd0Ln and the PdII-alkyl species, involving the inversion of the alkyl carbon, is also operative producing a detrimental effect in the enantioselectivity of the reaction.

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