Polycyclic Azetidines and Pyrrolidines via Palladium-Catalyzed Intramolecular Amination of Unactivated C(sp3)–H Bonds

A novel strategy to construct complex
polycyclic nitrogen-containing
heterocycles from aliphatic amines via picolinamide-assisted palladium-catalyzed
C–H bond activation reaction was reported. The reaction exhibits
broad substrate scope for the synthesis of various azabicyclic scaffolds,
including azetidines and tropane-class alkaloids. Application of this
method to naturally occurring (−)-cis-myrtanylamine,
an unprecedented type of carbon–carbon bond activation, in
which the electron-pair involved initiates an intramolecular “SN2-like” displacement of a cyclopalladium-fragment from
a tertiary center, is described.