Photoinduced SET for the functionalization of alkanes

Abstract

Thermochemical cycles show that deprotonation of alkane radical cations is an exothermic process, and indeed photoinduced SET between several alkanes and 1,2,4,5-tetracyanobenzene (TCB) is followed by efficient deprotonation of the radical cation with tertiary > secondary > primary selectivity; the alkyl radical is trapped by TCB˙^– or, when present, by oxygen; when tetrachloro-p-benzoquinone is used in the place of TCB, the radical is further oxidized to the cation.