Synthesis of 1,2-Diamines from Vinyl Sulfonium Salts and Arylamines

Abstract

A procedure for the synthesis of 1,2-diamines from vinyl sulfonium salts and arylamines under mild conditions was developed. This present synthetic protocol not only obviates the need for a transition-metal catalyst and an oxidizing reagent but also features a broad substrates scope. The practicability of this protocol is demonstrated by the one-pot synthesis, a scale-up reaction, and transformations of the products to diverse N-heterocyclic compounds. Mechanistic studies indicate that the formation of aziridine plays a key role during this diamination process.

Recent Advancements on Metal‐Free Vicinal Diamination of Alkenes: Synthetic Strategies and Mechanistic Insights

“…In 2022, Jian Wen and co‐workers demonstrated t BuOK‐KBr promoted diamination process with practicability in N ‐heterocycle synthesis and avoids necessity of transition‐metal catalyst and oxidizing reagent (Scheme 19). [91] In this transformation, vinyl sulfonium salts 90 were utilized as alkene source, and aryl amines 91 as nitrogen source. This innovative protocol can successfully accommodate well variety of styrene sulfonium salts 90 and aryl amines 91 with electron‐donating (CH 3 , C(CH 3 ) 3 , SCH 3 ) and electron‐deficient (F, Cl, Br, I, CF 3 ) substituents including multisubstitued ( 92 ap – 92 aw : 68‐77% and fused substrates ( 92 qa: 65% and 92 ax: 76% ).…”

Formal allylic C(sp3)–H alkylation of α-alkylstyrenes by rearrangement of intermediate alkenyl sulfonium salts

“…10 These elegant works led to our ongoing interest in research on alkenyl sulfonium salts. 11 Herein, we expand this reactivity to the allylic C(sp 3 )–H alkylation of branched α-alkenyl sulfonium salts. With this method, a wide range of branched α-alkenyl sulfonium salts were well tolerated, affording the corresponding products in moderate to excellent yields.…”

Regiospecific Alkene Aminofunctionalization via an Electrogenerated Dielectrophile

“…While vinyl and alkenyl sulfonium salts have been employed as electrophiles for diverse transformations, ,− ,− they have not been leveraged for single substitution as proposed herein. Indeed, selective single nucleophilic addition into these species to form a monosulfonium salt has only been observed in a handful of isolated instances as an undesired byproduct. ,,, Accordingly, we sought to validate that this species was indeed kinetically competent in the reaction.…”