Copper-Catalyzed Aerobic -Amination of Sulfenamides for the Synthesis of Sulfinamidines.

Herein, we present a copper-catalyzed oxidative amination of sulfenamides for the synthesis of sulfinamidines. By the employment of air as the terminal oxidant, a diverse array of secondary and primary amines can be efficiently transformed into their corresponding products. This method is well-suited for last-stage functionalization, and the underlying mechanism has been investigated.

Redox-Neutral Strategy for Sulfilimines Synthesis via S-Arylation of Sulfenamides.

In this investigation, an unprecedented transition-metal-free and redox-neutral synthesis of sulfilimines was realized through the S-arylation of readily obtainable sulfenamides employing diaryliodonium salts. The pivotal step encompassed the resonance between bivalent nitrogen-centered anions, engendered postdeprotonation of sulfenamides under alkaline conditions, and sulfinimidoyl anions. The experimental outcomes demonstrate that sulfinimidoyl anionic species function as efficacious nucleophilic reagents, affording sulfilimines with notable to exceptional yields and superlative chemoselectivity, all executed within a transition-metal-free protocol and under exceptionally mild conditions.

Redox-Neutral Synthesis of Sulfilimines through the S-Alkylation of Sulfenamides.

In this work, we developed a metal-free and redox-neutral strategy for the selective S-alkylation of sulfenamides under basic conditions to yield sulfilimines. The key step involves the resonance between bivalent nitrogen-centered anions, generated after deprotonation of sulfenamides under alkaline conditions, and sulfinimidoyl anions. Our sustainable and efficient approach employs sulfur-selective alkylation of readily accessible sulfenamides and commercially available halogenated hydrocarbons, resulting in the successful synthesis of 60 sulfilimines in high yields (36-99%) and short reaction times.

Hypervalent Iodine-Mediated Synthesis of Sulfinimidate Esters from Sulfenamides.

In this study, we present a novel and efficient approach for the oxidative esterification of sulfenamides using phenyliodonium diacetate, enabling the synthesis of sulfinimidate esters and sulfilimines under mild and metal-free conditions, with yields reaching up to 99%. The protocol is readily scalable and compatible with a diverse range of substrates and functional groups, and we demonstrate its potential for late-stage functionalization of pharmacologically relevant molecules. Furthermore, we propose a plausible reaction mechanism to account for the observed sequence of events.