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.