Acetone promoted 1,4-migration of an alkoxycarbonyl group on a syn-1,2-diamine

[Display omitted] •Acetone promoted isomerization of an amino mitosene.•Kinetic studies and DFT calculations.•Organocatalytic mechanism. A 2-protected cis-amino mitosene undergoes an irreversible acetone promoted isomerization and converts to the 1-isomer. Kinetic studies and DFT calculations of the reaction are reported. An organocatalytic mechanism is proposed, involving a covalent intermediate formed by reaction of the mitosene and acetone.