Rare examples of a synthetically useful radical ipso substitution of a carbon-fluorine bond are reported. Highly functionalized fluoroazaindoline structures have thus been prepared with use of cheap and readily available substrates and reagents.

A radical generated on the side-chain of a 2- or 4-N-alkylamino-4,6- or 2,6-dichloropyrimidine can cyclise on the nitrogen or on the carbon of the pyrimidine ring depending on its position and on whether an acetyl or a Boc group is present on the extra-nuclear nitrogen.