An intramolecular imination/azidation sequence has been realized through the tetrak-hexafluorophophate [Cu(CH 3 CN) 4 PF 6 ]-catalyzed reaction of g,d-unsaturated ketone O-benzoyl oximes with trimethylsilyl azide (TMSN 3 ). The reaction proceeds via the copper-mediated N À O cleavage and subsequent C À N forming 5-exo cyclization. The thus formed intermediate is then azidated to afford the corresponding dihydropyrrole product. Preliminary mechanistic investigations suggest that the cyclization step does not involve a radical intermediate.

Copper-Catalyzed Cyclization and Azidation of ,-Unsaturated Ketone O-Benzoyl Oximes. -Dihydropyrrole derivatives are synthesized through an intramolecular imination/azidation sequence starting from title oximes. The reaction mechanism is discussed. -(SU, H.; LI, W.; XUAN, Z.; YU*, W.; Adv. Synth. Catal. 357 (2015) 1, 64-70, http://dx.