An Aminative Rearrangement of O‐(Arenesulfonyl)hydroxylamines: Facile Access to ortho‐Sulfonyl Anilines

Abstract

Ortho-sulfonyl anilines are important building blocks for a range of applications. We report the discovery of an aromatic rearrangement reaction of O-(arenesulfonyl)hydroxylamines which leads directly to ortho-sulfonyl anilines through formation of a new CÀ N bond with excellent levels of regiocontrol for the ortho position(s) over all others. We establish that the rearrangement is proceeding through an intermolecular mechanism and propose that the regiocontrol observed is the result of attractive non-covalent interactions occurring during the CÀ N bond-forming step. Importantly, this method is complementary to classical aniline sulfonation in terms of the variously substituted regioisomers that can be obtained and it is also applicable to O-(benzylsulfonyl) hydroxylamines.

A Sulfonative rearrangement of N-Aryl Sulfamates to para-Sulfonyl Anilines

“…[25][26][27][28][29] An ortho-selective aminative rearrangement of (arenesulfonyl)hydroxylamines has recently been revealed. [30] Scheme 1. Initial attempts to prepare aniline sulfamates as their tributylammonium and sodium salts and resulting thermal rearrangement products.…”

“…In turn these sulfonated (hetero)aryl systems can be further manipulated to sulfonyl chlorides, sulfonamides, and sulfinates as building blocks in medchem. [30]…”