New synthetic methods via radical cation fragmentation

Photoinduced single electron transfer followed by radical cation cleavage is a selective method for generating radicals and cations from unconventional substrates under unparalleled mild conditions. The versatility of the method and its synthetic significance are demonstrated through the discussion of selected examples involving alkyl radicals as the key species, such as nucleophilic aromatic substitution, addition to unsatured esters, nitriles and ketones, and reduction, as well as of an example of addition to cations.