Confined Chiral Pd(II) Catalyst-Enabled Enantioselective Intramolecular Aminoalkylation of Alkenes: One-Step Construction of Chiral N-Fused Bicyclic Skeletons.

Highly enantioselective intramolecular aminoalkylation of unactivated alkenes has been accomplished for the first time through the development of a novel category of confined chiral Pd(II) catalysts consisting of two axially chiral picolinic acid ligands. A variety of polycyclic compounds, featuring a saturated chiral N-fused 6/5 or 7/5 bicyclic skeleton, were synthesized in moderate to good yields with excellent enantiomeric ratios (up to 99.5:0.5) through the formation of both a C-N bond and a C-C bond in a single synthetic step.