Kumada mechanistic studies

Chapter 4 describes the mechanistic studies on the palladium 1,2-migration in the Negishi and Kumada couplings, which were conducted under the guidance of Professor John F. Hartwig. The work has not been published so far. 

Mechanistic understanding of the Kumada coupling was expanded by the isolation of a nickel(I) intermediate by Matsubara and coworkers (Figiu-e 13.11) [17], and further investigated by Louie [18]. A niunber of experiments support the mechanistic hypothesis uivolvuig the generation of a nickel(I) species in the reaction between nickel(0)-NHC complexes with aryl halides. Fiuther studies... 

Numerous other metallic salts have been shown to exhibit similar reactivity profiles in the Kumada coupling, although not necessarily via the same mechanistic pathway. Even in the early studies of Kharasch, Kochi, Gilman and a variety of others, cobalt and iron salts displayed similar reactivity to... 

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