ChemInform Abstract: Rational Design in Homogeneous Catalysis. Ir(I)-Catalyzed Addition of Aniline to Norbornylene via N-H Activation.

ChemInform Abstract

A new approach to the synthetically important amination of olefins is demonstrated. The various steps are elaborated in a catalytic cycle. The initial N-H oxidative addition step is shown for the Ir complexes (I), Ir(PEt₃)₃Cl and (Ir(PMe₃)₄)PF₆, all of which give rise to stable cis anilido hydride complexes when reacted with aniline (II). The second step, olefin insertion, is accomplished from the reaction of (IV) with (II) and norbornylene (V). The resulting azametallacycle (VI) (obtained with ca. 90% purity in an overall yield of 50%) is characterized by NMR spectroscopy and X-ray diffraction (P2₁/c, Z=4). It decomposes in two competing pathways. The competing course of C-H reductive elimination occurs by prior ligand dissociation and yields the amination product exo-(VII).