Allylic Substitution versus Suzuki Cross‐Coupling: Capitalizing on Chemoselectivity with Bifunctional Substrates

One catalyst, two reactions—a tale of chemoselectivity : Given the choice between an allylic acetate and a vinylboronate ester, palladium preferentially reacts with the allylic acetate to give the allylic substitution product. In the presence of an aryl bromide and base, Suzuki cross‐coupling subsequently ensues to afford allylic amines (see scheme; pin=pinacol, THF=tetrahydrofuran).