Strain-release C-C bond cleavage enables the [2,3]-sigmatropic rearrangement of tertiary allylamines.

A new strategy has been established for the [2,3]-sigmatropic rearrangement of quaternary allylammonium ylides, generated in situ from tertiary allylamines and a bicyclo[1.1.0]butane via strain-release C-C bond cleavage. A range of tertiary allylamines with an acidic α-C-H bond participated in the 1-sulfonylbicyclo[1.1.0]butane-mediated [2,3]-sigmatropic rearrangement, delivering structurally diverse N-cyclobutyl homoallylamines in moderate to excellent yields.