Facet‐Dependent Catalytic Activity of Palladium Nanocrystals in Tsuji–Trost Allylic Amination Reactions with Product Selectivity

Pd nanocubes, cuboctahedra, and octahedra with good size control were used to catalyze CN bond formation in the Tsuji–Trost allylic amination reaction of aniline. Nanocubes gave either monoallylaniline or diallylaniline depending on the amount of allyl bromide used, but the octahedra and cuboctahedra only gave mixtures of monoallylaniline and diallylaniline under the same reaction conditions. The Pd nanocubes were stable over multiple cycles of the reaction. The cubes and octahedra were demonstrated to catalyze the amination reaction by using a wide variety of substituted anilines, but the cubes were the best catalyst with consistently the highest efficiency, product yield, and product selectivity. This work demonstrates that the use of metal nanocrystals with proper facet control is important for catalyzing coupling reactions with product selectivity.