The aromatic Cope rearrangement is an elusive transformation that has been the subject to limited number of investigations compared to these seemingly close analogues, namely the Cope and aromatic Claisen rearrangement. Inspired by moderate success observed in the course of pioneering works, we performed some investigations on this reaction. By carefull experimental and theoretical investigations, we demonstrate that key subtitutions on 1,5-hexadiene scaffold allows fruithful transformations. Especially, efficient functionalisation of heteroaromatic rings results from the aromatic Cope rearrangement, while highly stereoselective interrupted aromatic Cope rearrangement highlight the formation of chiral compounds throurought a dearomative process.

These data are the NMR raw data (primary NMR FID files) of all new compounds and of the kinetic experiments of this study.