Selective synthesis of alkyl amines and N-vinylazoles from vinyl sulfonium salts with N-nucleophiles

Abstract

Herein, we developed an efficient and green method for the synthesis of various alkyl amines via C(sp3)−S bond cleavage of vinylsulfonium salts. The reaction proceeds under an air atmosphere with...

Palladacycle-Catalyzed Olefinic C–P Cross-Coupling of Alkenylsulfonium Salts with Diarylphosphines to Access Alkenylphosphines

“…They have shown promise as a class of versatile electrophilic reagents for various transformations . Among them, alkenylsulfonium salts (R 1 CHCHS + R 2 R 3 X – ) had been quite limited until the discovery of the elegant preparation of alkenyl tetrahydrothiophenium and dibenzothiophenium salts (where R 1 was limited to aryls) and thianthrenium salts (where R 1 was expanded to alkyls and aryls), which significantly broadened the reaction scope and caused the related chemistry to flourish . We have made continuous efforts in C–P bond formation enabled by transition-metal catalysis, ,,, which led us to pursue an efficient olefinic C–P bond formation method for the synthesis of tertiary alkenylphosphines.…”

Transition‐Metal‐Free Olefinic C−H Azidoalkylthiolation via C(sp3)−S Bond Cleavage of Vinylsulfonium Salts

“…However, the analogs of aryl sulfonium salts, that is, vinylsulfonium salts, have been paid much less attention as applicable coupling partners [15] . Very recently, Wen and coworkers realized the synthesis of alkyl amines via the C( sp 3 )−S bond cleavage of vinylsulfonium salts [15g] . During the continuous exploration of the multiple reactivities of functionalized olefins, [12b,16] we recently achieved palladium‐catalyzed C−H fluoroalkylthiolation through C( sp 3 )−S bond cleavage of vinylsulfonium salts with CsF [17] .…”

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.…”