Palladium-Catalyzed Carbene Insertion into Vinyl Halides and Trapping with Amines

Palladium is shown to catalyze the three-component coupling of vinyl halides, trimethylsilyldiazomethane, and amines to generate allylamines. The mechanism is believed to involve formation of an R-Pd=CHSiMe3 intermediate that undergoes migration of the vinyl ligand to the empty p-orbital of the carbene ligand. The resulting eta1-allylpalladium species forms an eta3-allylpalladium intermediate that is trapped by the amine nucleophile. Under the conditions tested, cyclic secondary amines and terminal vinyl iodides give the best results.