Synthesis of C—N Axial Chirality N‐Arylindoles via Pd(II)‐Catalyzed Free Amine‐Directed Atroposelective C—H Olefination†

Comprehensive Summary Axially chiral N ‐arylindoles bearing a stereogenic C—N axis are unique important scaffolds in natural products, advance materials, pharmaceuticals and privileged chiral ligands or catalysts. Herein, we report the direct synthesis of C—N axially chiral N ‐arylindoles through a Pd‐catalyzed free amine‐directed atroposelective C—H olefination enabled by a spiro phosphoric acid (SPA) ligand. A wide range of enantioenriched N ‐aromatic amine indoles were obtained in high yields with good enantioselectivities (35 examples, up to 91% yield and up to 96% ee). The chiral products with free amine group offer an effective functional handle for down‐stream diversity‐oriented synthesis.