Enantioselective Olefin 1,2-Arylamination Catalyzed by a Planar Chiral Indenyl-Rhodium(III) Complex

We report an enantioselective 1,2-arylamination of unactivated alkenes catalyzed by a chiral indenyl-Rh-(III) complex using Troc-protected hydroxylamine derivatives. This method enables efficient access to structurally diverse 2-aminotetralin scaffolds and amino-substituted carbospirocycles via a 6-endo cyclization involving electrophilic aromatic substitution (EAS). Experimental and computational studies reveal that the electronic asymmetry of the chiral indenyl ligand plays a pivotal role in enhancing catalytic activity compared to cyclopentadienyl-based analogs. Furthermore, the identity of the N-protecting group on hydroxylamine significantly influences the reaction pathway, distinguishing this transformation from previously reported aziridination strategies. The synthetic utility and versatility of this catalytic system are further demonstrated through streamlined syntheses of biologically relevant molecules, highlighting its strong potential for applications in medicinal chemistry.