The generation of perfluoroalkyl radicals (RF•) by means of photocatalysis is a
more suitable route than the established methods employing chemical initiators, like azo or
peroxide compounds or the use of transition metals. Conditions governed by photocatalysis
can allow for a wide range of functional groups and, therefore, can be applied to the latestage
transformation of bioactive molecules. Organic photocatalysts (POC), in the absence of
transition metals, can suffer electron-exchange reactions, yielding RF radicals. RF radical
production without the assistance of transition metals through the employment of POC will
be described, applying this methodology to studying classical examples.