Asymmetric 1,n‐Remote Aminoacetoxylation of Unactivated Internal Alkenes Enabled by Palladium Catalysis**

Abstract A palladium‐catalyzed asymmetric 1,n‐remote aminoacetoxylation of cis ‐alkenes has been developed using PhI(OAc) 2 as an oxidant, providing the acetoxylated lactams with excellent enantioselectivities under mild reaction conditions. The sterically hindered pyridine‐oxazoline (Pyox) L3 with a tert ‐butyl group in oxazoline ring and propyl group in C6 position of pyridinyl is vital for the reaction, where the former is good for asymmetric aminopalladation step and the latter for the chain walking process. The enantioenriched lactam products were proven to be good building blocks for the synthesis of azabicycles.