Palladium-Mediated Cγ -H Functionalization of Alicyclic Amines.

This paper describes a new method for the transannular functionalization of the γ-C-H bonds in alicyclic amines to install C(sp3 )-halogen, oxygen, nitrogen, boron, and sulfur bonds. The key challenge for this transformation is controlling the relative rate of Cγ -H versus Cα -H functionalization. We demonstrate that this selectivity can be achieved by pre-complexation of the substrate with Pd prior to the addition of oxidant. This approach enables the use of diverse oxidants that ultimately install various heteroatom functional groups at the γ-position with high site- and diastereoselectivity.