In this study we have demonstrated that TBSAB is an efficient aniline N-sulfamation reagent and mild sulfamate to sulfonate relay reagent. A range of aniline and heterocyclic scaffolds were sulfonated in high conversions (6 examples of N(sp 2 )-sulfamates up to 99% isolated yield and 16 examples of C(sp 2 )-sulfonate in up to 80% isolated yield) with the ability to change the ortho-para ratio of the products obtained under thermal control. A re-investigation of the N-to C-sulfate rearrangement mechanism through designed examples with variation at the heteroatom position, and kinetic isotope experiments (KIE H/D ) confirmed the necessity of an N-sulfamate intermediate.