Finally, we evaluated the substrate scope and compared the product selectivity between AC and DC electrolysis in Figure . For all substrates, we performed AC electrolysis under fexp and DC electrolysis. For N-aryl pyrrolidine bearing electron-donating groups such as methyl, tertiary butyl, 2,6-dimethyl, indane, dioxole, ethylacetate and phenyl, the arylation product yields were significantly improved from 5-30% under DC electrolysis to 43-68% under AC electrolysis (1a, 7a-14a) while the cyanation product yields dropped from 11-40% to 0-38% (1b, 7b-14b). The product selectivity shifted from the cyanation products under DC electrolysis to the arylation products under AC electrolysis. The N-aryl pyrrolidine substituted with electron-withdrawing groups such as F, Cl, and Br also afforded one-electron transfer products (15a-17a) with greater selectivity and yields under AC electrolysis than the DC counterpart. In the case of N-aryl pyrrolidine without any substituent on ring (18) afforded poor yield (<20%) and selectivity in both electrolysis conditions (18a and 18b). The reaction of sixmembered cyclic amine, N-aryl piperidine 19, with 2 under both AC and DC electrolysis conditions provided poor yield for 19a and 19b, possibly because the impaired overlap between the lone pair of amine and the unpaired electron at the α-carbon significantly destabilizes the α-amino radical intermediate. Encouraged by the broad generality of our approach on five-membered cyclic amines, we tested it on another class of tertiary amines, N-aryl tetrahydroisoquinoline. Tetrahydroisoquinoline alkaloids are an important class of bioactive natural products and display a myriad of biological activities. N-aryl ring bearing electron-donating and electron-withdrawing groups such as methoxy, fluoro, dioxine, dimethyl, trifluoromethyl (20-26) and N-benzyl (27) all afforded arylated and cyanation products (20a-27a and 20b-27b). Under DC electrolysis, formation of cyanation product was predominantly observed in good yield 36-63% because the benzylic position is prone to overoxidation to form iminium cation. Under AC electrolysis, arylation product formation significantly improved to good/moderate yields of 26-51%. However, the cyanation product yields were comparable to the DC electrolysis results, even though the CV data in Figures S27-34 predicts that the two-electron oxidation of N-aryl tetrahydroisoquinolines should be largely reduced at fexp, like the N-aryl pyrrolidine oxidation. A possible explanation for the discrepancy is that there are alternative pathways to generate iminium cations that does not require NaOAc, for example, via deprotonation by in situ generated CN or dicyanobenzene 2. This explanation is in part supported by the formation of arylation and cyanation products at moderate yields for tetrahydroisoquinoline 20 even in the absence of NaOAc (Table ).