Our initial investigations focussed on preparing the anticipated key N(sp2)-aniline sulfamate as both the tributylammonium and sodium salts to explore whether there are any counterion differences (Scheme 1). Scheme 1. Initial attempts to prepare aniline sulfamates as their tributylammonium and sodium salts and resulting thermal rearrangement products. Following a single reported example of aniline sulfamation, we were able to prepare 2a in 91% yield as its tributylammonium salt (Scheme 1). Treatment of 2a with sodium iodide afforded the corresponding sodium salt, 3a in quantitative yield. Refluxing 2a and 3a in 1,4-dioxane, a trace (3% isolated) pararearrangement product (4a) with the tributylammonium counterion and no rearrangement with the sodium counterion. Thus, indicating the suitability of the tributylammonium counterion for further exploration.