[a] Yields were determined by 1 H NMR using 1,1,2,2-tetrachloroethane as an internal standard. Reactions performed on a 0.1 mmol scale in anhydrous MeCN. [b] 1a (1.5 equiv.) and 2a (1.0 equiv.) in MeCN (0.1 M). n.d. = not detected. The relative underperformance of the 3,3-diphenylpropanoic acid derivative to give product 5 is likely due to the reactive diaryl benzylic C(sp )-H bond (BDE ≃ 84 kcal/mol for diphenylmethane), which may facilitate competitive side reactions or degradation pathways. Subsequently, various RAEs bearing functional groups at the para-position of the arene moiety were subjected to the reaction conditions. Both electron-withdrawing (Br, Cl, carboxylic ester, trifluoromethyl) and electron-donating groups (methoxy) were well tolerated, affording the functionalized amide products in good yields (9-14). The protocol also efficiently engaged α-oxy radicals and substrates with an alkynyl moiety (15 and 16). Importantly, examination of both secondary and tertiary radical precursors revealed the generality of our method, leading to corresponding difunctionalized products in satisfactory yields (17-19). Notably, although the conditions with TFA resulted in no detectable product when using the Boc-protected piperidine-4-carboxylic acid derivative, the simple switch to the Zn additive (Table , entry 5) tolerated the sensitive substrate, affording the product in a useful yield (20). Next, we aimed to further apply our conditions to different aromatic olefins (Figure ). Several electron-poor styrenes were successfully difunctionalized in the three-component process, including both para-(F, Cl, Br, carboxylic methyl ester) and ortho-(F) substituted acceptors in moderate to good yields (21-23, 25-27). To our delight, α-methyl 4-trifluorostyrene, styrene and 4-tert-butyl styrene were engaged as SOMOphiles, presenting the amide products in moderate yields (24, 28 and 29). 4-Acetoxystyrene and 1-(chloromethyl)-4-vinylbenzene yielded the desired products chemoselectively, without observing ester hydrolysis or dechlorination of the benzylic chloride moiety (30-31). As for the nitrile variation, a limitation of the scope was observed: in fact, only deuterated acetonitrile and propionitrile were found to be suitable reactants for altering the amidic portion (32 and 33). Other nitriles failed due to their inability to solubilize RAE substrates, even after irradiation with blue LEDs for 16 h. Intriguingly, the developed photocatalytic conditions were found to be applicable to agrochemically-and pharmaceutically-relevant motifs. For example, 2,4-dichlorophenoxy acetic acid and Gemfibrozil were converted into their NHPI derivatives and used to carboamidate 2a. On the other hand, (L)-Menthol and Ibuprofen containing olefins successfully reacted with RAE 1a. Thus, a desired synergy of LSF with Ritter-type processes was achieved in good yields (34-37). While exploring the scope of aryl olefins, the reaction between 1a and 1,1-diphenylethylene (DPE, 3a) gave no trace of the target carboamidated product in the crude reaction mixture. Instead, Heck-type product 38 was observed in 55% yield (Table , entry 1). This serendipitous outcome was unexpected, especially given that prior studies in the literature, including reports from the groups of Glorius, Doyle, Nagao and Ohmiya all achieved photoredox-catalyzed difunctionalization of DPE with nucleophiles such as water, 37,55 alcohols, fluoride, and sulfoximines. Presumably, in these protocols the nucleophiles efficiently engage the incipient benzylic carbocationgenerated via tandem radical addition and oxidative RPC stepsbefore deprotonation at the β-position occurs. This result underscored a limitation for the initially targeted Ritter-type difunctionalization. However, in our view it presented an intriguing example of photocatalytic chemodivergence. Figure : Scope of the Ritter-type olefin carboamidation using redox active esters. Reaction conditions: redox active ester 1 (0.3 mmol, 1.0 equiv.), aryl olefin (0.36 mmol, 1.2 equiv.), 4-CzIPN (5 mol%), TFA (10 equiv.) in the corresponding nitrile (0.1 M) as reaction solvent. For further details, see the Supporting Information. Isolated yields are reported.