Upon SET reduction, the entropically-driven fragmentation of 1 generates CO2, phthalimide anion and alkyl radical I. The latter then engages in a Giese-type addition to 2 or 3, yielding benzylic radical intermediate II (E1/2 ≃ from +0.23 to +0.73 V vs SCE). Subsequently, this is oxidized by 4-CzIPN •+ (E1/2 = +1.49 V vs SCE) in the RPC step, yielding carbocation III and closing the photocatalyst cycle. At this point, for the carboamidation III is trapped by the nitrile, forming nitrilium ion IV. Hydrolysis of the latter may proceed via nucleophilic attack by trifluoroacetate, forming the trifluoroacetimidate V, which finally undergoes deacylation to yield the difunctionalized product and trifluoroacetic anhydride (TFAA). Alternatively, adventitious water present in TFA hydrolyses the nitrilium ion as per a classical Ritter reaction. For the Heck-type process, deprotonation of III by the phthalimide anion yields the Heck-type product. The corresponding carboamidated products were not detected with 1,1-diarylolefins in the presence of MeCN (cf. Table , entry 1), likely due to lower electrophilicity and enhanced hindrance of the diarylbenzylic cation. An alternative pathway for the Heck-type reaction could involve a radical chain with inefficient propagation, deriving from SET between the incipient diaryl benzylic radical VI (E1/2 ≃ -1.34 V vs SCE) and 1, leading to the formation of the benzylic cation VII and I (Figure ). Although quantum yields measured did not accord with this proposal, values of Φ < 1 do not completely rule out chain pathways. Finally, we demonstrated the scalability of our divergent process, in both batch and continuous flow (Figure ). Regarding batch experiments, a simple set-up involving two Kessil lamps (456 nm, 50% intensity) enabled production of half a gram of carboamidation product 4. Additionally, the Heck-type reaction was achieved on a 4 mmol, gram-scale synthesis of 60, a product highly attractive for post-functionalization due to the presence of two C(sp 2 )-Br bonds. Continuous flow technology was leveraged, facilitating rapid and efficient scale-up of both carboamidation and Heck-type products. In fact, under optimized conditions, a residence time (τ) of just 100 minutes was sufficient, notably decreasing reaction time compared to the 16 h batch process (for further details see Supporting Information, section 9.2). With this approach, amide products 10, 22, and 37 were successfully synthesized on a 1 mmol scale, while trisubstituted alkene product 47 was produced on a 4 mmol scale, demonstrating in both cases satisfactory overall space time yields (up to 36 mmol L -1 h -1 ).