Kumada Coupling - Scope - Organic Halides and Pseudohalides

Organic Halides and Pseudohalides

The Kumada coupling has been successfully demonstrated for a variety of aryl or vinyl halides. In place of the halide reagent pseudohalides can also be used, and the coupling has been shown to be quite effective using tosylate and triflate species in variety of conditions.

Despite broad success with aryl and vinyl couplings, the use of alkyl halides is less general due to several complicating factors. Having no π-electrons, alkyl halides require different oxidative addition mechanisms than aryl or vinyl groups, and these processes are currently poorly understood. Additionally, the presence of β-hydrogens makes alkyl halides susceptible to competitive elimination processes.

These issues have been circumvented by the presence of an activating group, such as the carbonyl in α-bromoketones, that drives the reaction forward. However, Kumada couplings havealso been performed with non-activated alkyl chains, often through the use of additional catalysts or reagents. For instance, with the addition of 1,3-butadienes Kambe and coworkers demonstrated nickel catalyzed alkyl-alkyl couplings that would otherwise be unreactive.

Though poorly understood, the mechanism of this reaction is proposed to involve the formation of an octadienyl nickel complex. This catalyst is proposed to undergo transmetalation with a Grignard reagent first, prior to the reductive elimination of the halide, reducing the risk of β-hydride elimination. However, the presence of a Ni(IV) intermediate is contrary to mechanisms proposed for aryl or vinyl halide couplings.