Asymmetric Formation of Allylic Amines with N‐Substituted Quaternary Stereocenters by PdII‐Catalyzed Aza‐Claisen Rearrangements

With the ferrocene imidazoline palladacycle FIP-Cl as precatalyst, quaternary N-substituted stereocenters can be generated in an asymmetric aza-Claisen rearrangement. Excellent enantioselectivities are obtained even if R and R′ have a similar or identical size (see scheme: e.g. 96 % ee for CH3/CD3).