Azasulfur(iv) derivatives of sulfite and sulfinate esters by formal S–S bond insertion of dichloramines

Abstract

Azasulfur(VI) compounds such as sulfoximines and sulfonimidamides are attractive due to the unique properties of the SN bond. While the synthesis of these carbon-attached sulfonimidoyl derivatives is well-established, the situation is different for their heteroatom-bound counterparts. In this work, we propose azasulfur(IV) esters as platform chemicals that can be derivatized to obtain all types of S^VIN functional groups, among these are the poorly accessible, all-heteroatom imidosulfate esters. Using a chloroamination workflow established here, S–S bond-containing structures such as elemental sulfur or diaryl disulfides can be transformed into imidothionyl or sulfinimidoyl chlorides, which are easily esterified or amidated. Thus, chloramines serve as a versatile [N] and [Cl⁺] source, and by using them in the context reported here, we advance the set of mild synthetic methods as the latest toolbox member to cover even more of the azasulfur(IV) and (VI) chemical space.