Here we report the reaction of diaryl substituted esters with frustrated Lewis pairs. Interestingly this results in divergent pathways, one whereby the diaryl moiety is stabilized by the Lewis basic phosphine or the alternative pathway, wherein a single-electron transfer process occurs generating the [Mes₃P]^+·/[C(H)Ar₂]^· radical ion pair. The latter species undergoes a homocoupling reaction to yield tetraphenylethane derivatives. In the presence of olefins, this reactivity can be harnessed through an sp²-sp³ C–C heterocoupling reaction to generate α,β-substituted olefins. Notably, this work showcases a frustrated Lewis pair approach to metal-free radical C–H bond activation with subsequent C–C bond formation which also displays complementary reactivity to other approaches. Data includes description of experimental procedures, NMR data and X-ray data.

Research results based upon these data can be found at https://doi.org/10.1016/j.xcrp.2020.100016