The scope of stereocontrolled alkene hydrothiophosphorylation was also investigated, as outlined at the bottom of Table 2. A variety of unactivated alkenes provided products with yields ranging from 65% to 83%, exhibiting excellent diastereoselectivity (at P). The mild conditions facilitated high chemoselectivity, with functional groups such as phosphonates being well-tolerated, resulting in bisphosphonate products (25-26) in high yields (65% and 72%). Compounds containing protected amines also showed high compatibility with the method (27 and 33). Additionally, alkenes with electron-withdrawing groups are also accom-modated (28). Functional groups that are typically challenging in transition metal-catalyzed reactions, such as Bpin (34), were also well-tolerated. Moreover, medicinally relevant functionalities, including nucleosides and phosphorylated-PEG derivatives (31 and 35) were investigated. Lastly, it was found that the hydrophosphorylation of alkenes tolerates esters (29 and 32). The most interesting aspect of this study is the bifurcated reactivity of the P(V)-reagents that can be modulated mainly by changing the anode employed. A mechanistic picture and supporting experiments to explain the unique reactivity exhibited in both olefin and carbonyl hydrophosphorylation is illustrated in Figure . The key role of the pentafluorothiophenol as leaving group is demonstrated by its reduction potential (-1.35 V) as compared to di-Hydro-Br-Y (see panel [A] for CV). The electron-deficient nature of the arene enables the unveiling of the P-centered radical presumably via dissociative electron transfer at an accessible reduction range. It is in this step that added DMSO can assist in completing the electrolytic cycle as a sacrificial reductant. The P-centered radical can be regenerated as well from 36 via anodic oxidation when a non-sacrificial anode is employed (Pathway B). In either case, formation of 36 was observed as a side product and in the absence of a radical acceptor, it was the major product. In the case of carbonyl phosphorylation (Abramov reactivity) formation of 36 is again invoked as above. We postulate that this species adds to carbonyl compounds non-electrochemically in the presence of Zn(II) salts released from the sacrificial anode. To test this hypothesis, non-electrochemical experiments were performed; 36 underwent carbonyl hydrophosphorylation in the presence of ZnBr2 whereas no product was observed in its absence (panel [E]).