A Highly Enantioselective Overman Rearrangement through Asymmetric Counteranion‐Directed Palladium Catalysis

The chiral TRIP anion combined with a simple commercially available palladacycle furnishes a highly active catalyst for the enantioselective rearrangement of allylic imidates to the corresponding amide products in high yields (see scheme). The stereoselectivity is induced entirely by the chiral phosphate anion although the catalyst complex contains a chiral palladacycle (see scheme).