Isothiocyanates (in situ) and sulfonyl chlorides in water for N-functionalization of bicyclic amidines: access to N-alkylated γ-/ω-lactam derivatized thiourea and sulfonamides

Abstract

Herein, we showcase the potential of isothiocyanates generated in situ and aryl sulfonyl chlorides as electrophiles in water for N-functionalization of bicyclic amidines (DBN and DBU). This strategy provides complementary access to a range of thiouredosulfides, sulfonamides, aroylthioureas and amides derivativatized with distal γ- and ω-lactams. A novel sulfonyl chloride mediated formation of β-uredo sulfides has been achieved from β-isothiocyanato sulfides, removing the requirement for the harsh synthesis of unstable isocyanates. Mechanistic studies suggest a radical mechanism for the difunctionalization of alkenes, the efficacy of H₂O in the ring opening of bicyclic amidines, and an oxygen source along with sulfonyl chloride as desulfurization agents for thiourea to afford urea derivatives.