1,3-Diaza-Claisen Rearrangements of Vinyl Pyrrolidines Tethered to In Situ Generated Carbodiimides Afford Ring-Expanded [9,5]- and [9,6]-Bicyclic Guanidines.

Vinyl pyrrolidines tethered to isothioureas are activated to the corresponding carbodiimides with AgOTf and EtN. Intramolecular addition of the vinyl pyrrolidine amine to the carbodiimide followed by a 1,3-diaza-Claisen rearrangement affords [9,5]- and [9,6]-bicyclic guanidines depending on the tether length in good to excellent yields. Density functional theory calculations reveal that the pathway involving intramolecular addition of the amine to carbodiimide to afford a zwitterionic intermediate followed by the zwitterionic 1,3-diaza-Claisen rearrangement was consistently a higher energy pathway than the path involving protonation of the zwitterionic intermediate followed by the cationic 1,3-diaza-Claisen rearrangement.