Toward an Improved Understanding of the Unusual Reactivity of Pd0/Trialkylphosphane Catalysts in Cross-Couplings of Alkyl Electrophiles: Quantifying the Factors That Determine the Rate of Oxidative Addition


  • Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R01-GM62871 to G.C.F. and R01-GM57034 supplement to I.D.H.), the American Chemical Society (Organic Division Fellowship to I.D.H., sponsored by Abbott Laboratories), the Natural Sciences and Engineering Research Council of Canada (Postdoctoral Fellowship to M.R.N.), Merck, and Novartis. Funding for the MIT Department of Chemistry Instrumentation Facility has been furnished in part by NSF CHE-9808061 and NSF DBI-9729592. We thank Johnson Matthey for supplying palladium compounds.


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What a difference a ligand makes! The reactivity of Pd0/trialkylphosphane complexes is of great interest because of their unusual effectiveness as cross-coupling catalysts for alkyl electrophiles [Eq. (1)]. This study sheds light on various aspects of the critical oxidative-addition step of the catalytic cycle.