Shapeshifting Gabriel Amine Synthesis with Iodo-BCPs

The Gabriel amine synthesis is a textbook method for the preparation of primary amines from alkyl halides. In this work, we demonstrate a Gabriel amine synthesis with iodo-bicyclopentanes to make aminomethyl bicyclobutanes. DFT studies support the concerted rearrangement of a bicyclo[1.1.1]pentyl to a bicyclo[1.1.0]butyl carbocation, initiated by a carbon-halide dissociation. A carboxamide substituent stabilizes the carbocation intermediate with anchimeric assistance.