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Advancing the mechanistic understanding of an enantioselective palladium-catalyzed alkene difunctionalization reaction.

ABSTRACT: The mechanism of an enantioselective palladium-catalyzed alkene difunctionalization reaction has been investigated. Kinetic analysis provides evidence of turnover-limiting attack of a proposed quinone methide intermediate with MeOH and suggests that copper is involved in productive product formation, not just catalyst turnover. Through examination of substrate electronic effects, a Jaffé relationship was observed correlating rate to electronic perturbation at two positions of the substrate. Ligand effects were evaluated to provide evidence of rapid ligand exchange between palladium and copper as well as a correlation between ligand electronic nature and enantioselectivity.

SUBMITTER: Jensen KH

PROVIDER: S-EPMC3066298 | biostudies-literature | 2010 Dec

REPOSITORIES: biostudies-literature

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Advancing the mechanistic understanding of an enantioselective palladium-catalyzed alkene difunctionalization reaction.

Jensen Katrina H KH Webb Jonathan D JD Sigman Matthew S MS

Journal of the American Chemical Society 20101117 49

The mechanism of an enantioselective palladium-catalyzed alkene difunctionalization reaction has been investigated. Kinetic analysis provides evidence of turnover-limiting attack of a proposed quinone methide intermediate with MeOH and suggests that copper is involved in productive product formation, not just catalyst turnover. Through examination of substrate electronic effects, a Jaffé relationship was observed correlating rate to electronic perturbation at two positions of the substrate. Liga ...[more]

PMID: 21082845

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