Palladium‐Catalyzed Alkene Carboamination Reactions of Electron‐Poor Nitrogen Nucleophiles

Modified reaction conditions that facilitate Pd‐catalyzed alkene carboamination reactions of electron‐deficient nitrogen nucleophiles are reported. Pent‐4‐enylamine derivatives bearing N ‐tosyl or N ‐trifluoroacetyl groups are coupled with aryl triflates to afford substituted pyrrolidines in good yield. These reactions proceed via a mechanism involving anti ‐aminopalladation of the alkene, which differs from previously reported analogous reactions of N ‐aryl‐ and N ‐Boc‐pentenylamines. The application of these conditions to a formal synthesis of (±)‐aphanorphine is also described.