Exoselective 1,3-Dipolar [3 + 6] Cycloaddition of Azomethine Ylides with 2‑Acylcycloheptatrienes: Stereoselectivity and Mechanistic Insight

A highly exo-selective 1,3-dipolar [3 + 6] cycloaddition of azomethine ylides with 2-acylcycloheptatrienes was realized with a Cu­(I)/(S,Rp)-PPF-NHMe complex as the catalyst, leading to a diverse range of bridged piperidines with multiple functionalities in good yield with excellent stereoselectivity control. Theoretical calculations indicated a stepwise mechanism for this exo-selective [3 + 6] annulation, which accounts for the remarkable feature of this annulation: all of the larger substituent groups occupy the axial positions in the six-membered chairlike conformation of the piperidine ring.