Catalytic Enantioselective Synthesis of 4-Amino-5-aryltetrahydro-1 H -benzo[ c ]azepines by an Aminoarylation Reaction.

A one-pot asymmetric aminoarylation reaction has been executed for the synthesis of trans -4-amino-5-aryltetrahydrobenzo[ c ]azepines with excellent diastereo- and enantioselectivity (dr > 99: 1; ee ≤97%). The reaction progresses through aziridination of prochiral N -tosyl- N -cinnamylbenzylamines, followed by an intramolecular 7-endo-tet Friedel–Crafts cyclization of the tethered aziridines generated in situ, where the combination of Cu(OTf)₂ as a catalyst and PhINNs as a nitrene source was found to be effective. A chiral indenyl bis(oxazoline) was shown to be an efficient ligand for the catalytic enantioselective version of this one-pot transformation. This 7-endo-tet cyclization is contrary to the Baldwin cyclization rules. [ABSTRACT FROM AUTHOR]