We became motivated to turn DPE's inability to undergo the three-component transformation (consistent with preliminary observations reported by the groups of Akita and Song, Li) into an advantage. Thus, we sought to optimize the Heck-type reaction of 1,1-diarylolefins (for further information, see Supporting Information, section 5.2). To our surprise, the reaction proceeded in the absence of TFA, albeit in a lower yield (Table , entry 2), suggesting a divergence in the activation mechanism of RAEs (cf. Figure ). During the solvent screening, it was initially observed that anhydrous DMF without additives afforded 38 with comparable efficiency to that achieved under acidic conditions in acetonitrile (entry 3). Intriguingly, the reaction demonstrated higher yields when using analytical grade DMF as received by the supplier, thereby obviating the tedious need to dry and distill the reaction solvent (entry 4). Reversing the stoichiometry of 1a and 3a gave a similar, albeit marginally lower yield (entry 5 vs entry 4). Such conditions give flexibility to avoid unreacted excess DPE which can pose challenges in purification of certain substrates due to co-elution with target products (e.g. starting from not bearing aryl groups radical precursors). With optimized conditions in hand (entries 4 and 5), we set out to evaluate the generality of our method, which differs from the existing literature strategies to access similar Heck-type products as it requires neither transition metal-based photocatalysts, nor additives such as exogenous acids or bases. We began by applying the protocol to different RAEs (Figure ). Firstly, slight modifications to the standard NHPI ester 2a were explored, resulting in good yields of products (39 and 40) when employing para-methoxy and gem-diphenyl analogues.