In addition, the viability of electrochemical sulfinylation on aryl bromides bearing an electron-withdrawing group was showcased, including nitrile , sulfone , ketone , and ester functionalities. In these cases, 2 equiv of NFSI was used for the fluorination step. Furthermore, the preparation of substituted 3-and 4-pyridine sulfonyl fluorides from the corresponding iodides were also successful in the presence of an electron-donating group, such as a 2-methoxy (28, 30) and a 2-amino group (29), despite 3-iodopyridine only delivered 36 in 25% yield. These were found to be challenging under Pd conditions as well, which only delivered 28 and 29 in modest 28% and 21% yield, respectively. Meanwhile, a few unsuccessful examples are listed to acknowledge the limitations of the current method, which gave low yields in the presence of a phenol , an aldehyde or a nitro group . Only trace amount of sulfonyl fluorides was recorded when β-iodostyrene (34) and 4-iodo-1-methylpyrazole (35) were employed. To further highlight the excellent selectivity and versatility of the current method, 4-iodophenylboronic acid pinacol ester was subjected to e-sulfinylation, as depicted in Figure . Although typical fluorination of sulfinate 38 resulted in partial substitution on the boronic ester, the addition of KHF2 (4 equiv) enabled its full conversion into trifluoroboratea versatile functionality in cross-coupling reactions. The preservation of the C-B bond enabled efficient access to the bifunctional sulfonyl fluoride 39 in a 57% overall isolated yield. Meanwhile, the two benchmarked Pd conditions reported by the Ball and Willis laboratories, with the addition of KHF2, delivered 39 in 24% and 50%, respectively. Whilst the sulfinylation of aryl boronic acids using metal catalysis has been well documented, for instance, 4-iodophenylboronic acid was converted into 4-iodobenzene sulfinate using a Ni catalyst, 14 this method demonstrates an orthogonal reactivity for accessing sulfinylated product carrying a cross-coupling handle. The capability of further coupling reactivities would make 39 another candidate as SuFEx building block for the quick installation of arylsulfonyl fluoride module. 74 On the other hand, sulfinate 38 can be alkylated by 4-methylbenzyl bromide to produce sulfone 40 directly in 62%. Finally, a sulfonamide, a functional group commonly found in active pharmaceutical ingredients, could also be accessed easily through a sulfonyl chloride generated in situ, as evidenced by the formation of 41 in 51%. All these transformations of sulfinate 38 were conveniently performed in a one-pot mannerno additional work up is needed prior to the derivatizations, hence proving the compatibility of various ingredients in e-sulfinylation with these downstream reactions. and supporting information for comparison conditions, followed by the addition of aq. KHF2 (4 equiv).