The reaction of per(poly)fluoroalkanesulfonyl azides with tertiary and secondary amines: generation and trapping of enamines

Per(poly)fluoroalkanesulfonyl azides decomposed readily at 0°C or ambient temperature in the presence of tertiary or secondary amines via a single electron transfer process and gave the corresponding fluoroalkanesulfonyl amides and N-fluoroalkanesulfonyl amidines. The formation of amidines was reasonably explained in terms of trapping of N-substituted vinylamine generated in situ with the azides.