( due to chemoselectivity concerns. Changing the electrode parameters to (+)RVC/(-)RVC and (+)Mg/(-)RVC dramatically reduces the reactivity (entries 3-4). Addition of TFA (entry 5) as proton source or replacement of TTMSS with Ph3SiH (entry 6) shut down the reaction. Control studies (entries 7-8) demonstrated the need of TTMSS and electricity. Lastly it was found that the ratio between P(V) reagent (2) and TTMSS are essential to obtain the product in high yields (entries 9-11) With a robust set of optimized conditions in hand for these two transformations, the substrate scope was explored as depicted in Table . The 1,2-phosphorylation conditions were found to be general for ketones bearing several different substituents including ethers (5 and 8, 70% and 65% respectively), protected amines (6, 81%), and strained ketones (5-7, 48-81%). Although adducts 5-8 were obtained in relatively high yields, decomposition back to the parent ketone was observed during workup which explains the difference between the 31P NMR and isolated yields (see SI). Various categories of aldehydes (9-24) were also explored in this study, including benzylic aldehydes (10-13), unconjugated aldehydes with a variety of ring sizes (14-24), and a-heteroatom-substituted aldehydes (21, 24, and 9). The relatively high functional group tolerance suggests that this methodology could also be applied to substrates of biological interest, such as nucleotide bioisosteres (9) and amino acid bioisosteres (19-21 and 24) in preparatively useful yields (28-89%). As alluded to above, the main limitation of this reaction is the stability of the products themselves as many ketone and aldehyde substrates (see SI) simply revert back to starting material upon workup and purification. Attempts to further derivatize the adducts using DBU and a nucleophile similarly led to ketone. Importantly, although the stereochemical result at P was completely controlled, the diastereoselectivity at C of the adducts was generally not (usually ca. 1:1).