Acetic Anhydride Mediated Retro-Ene Reaction via a [4.4.3]Propel­lane Skeleton Intermediate Containing a Quaternary Ammonium Linkage

A novel retro-ene reaction via a [4.4.3]propellane intermediate containing a quaternary ammonium linkage was developed. The feature of this acetic anhydride mediated rearrangement includes the elimination of an acetoxy group at the C14 position and subsequent intramolecular nucleophilic addition of a nitrogen functional group to form an isolable ammonium salt intermediate. We clarified the reaction mechanism utilizing the deuterated derivative.