A new synthesis of N,N-bis(trimethylsilyl)enamines from straight chain olefinic amines has been devised which makes use of iron pentacarbonyl photocatalysed isomerisation. Complete conversion of the olefinic amines to the enamines was observed for substituted N,N-bis(trimethylsilyl)allylamines and non-allylic amines. The enamines obtained are potential sources of aldehydes and precursors of substituted