Sulfamated (N(sp 2 )-SO3) and sulfonated (C(sp 2 )-SO3) arylated motifs are found in a variety of valuable commodities including sulfa dyes, sulfa drugs and bioactive molecules (Figure ). Examples of bioactive N(sp 2 )-sulfamates include A) a sulfamate salt prodrug derivative of the potent and selective 2-(4-aminophenyl)benzothiazole anti-cancer agent; B) a malonate templated sulfamic acid phosphotyrosine mimetic as a selective and potent inhibitor of HPTPβ (a protein tyrosine phosphatase); C) a glycomimetic that has protective effects against lipid-induced endothelial dysfunction, restorative effects on diabetic endothelial colony forming cells, and preventative effects on downstream vascular calcification. [3] Examples of bioactive C(sp 2 )-sulfonates include: D) suramin, an approved medication for treating river blindness and African sleeping sickness; [4] E) an inhibitor against coenzyme A binding site of choline acetyltransferase and F) an indole derivative possessing PGD2 receptor antagonist activity. Furthermore, the mechanism by which sulfur trioxide (SO3) is transferred in a SEAr reaction to afford these type of aryl C(sp 2 )-sulfonate has been of perennial interest and reinvestigated by several groups. In turn, methods to prepare these N(sp 2 )-sulfamated precursors are limited and C(sp 2 )-sulfonated compounds are often only achievable under more forcing conditions (Chart 1). An ortho-selective aminative rearrangement of (arenesulfonyl)hydroxylamines has recently been revealed. Chart 1. Previous Approaches towards the synthesis of p-aminobenzene sulfonic acid compounds using an N-to C-SO3 transfer and This Work: using TBSAB to introduce SO3 group into aromatic systems.