Abstract The stereochemical course of the thermal 2-aza-Cope rearrangement of the optically pure acyl azide (−)-(1S)-5 was investigated by determination of the absolute configuration of the rearrangement product (1R, 8S)-9. The reaction proceeds by a sequence of stereospecific steps from 5 to an equilibrating mixture of exo-and endo- isocyanates 6 and 7. The endo-isomer 7 undergoes Cope rearrangement to the putative ...