Redox isomerization reaction wherein N-alkylpropargylamines are converted into N-alkylideneallylamines in the presence of rhenium(I) complexes as catalysts is described. Among the additives tested, certain pyridine N-oxides and tertiary amine N-oxides were effective for the reaction to proceed, and in particular, the use of 2,6-lutidine N-oxides gave the best results. The choice of a diphenylmethyl group as a substituent on the nitrogen atom was key to the success of the reaction, allowing it to reach completion.