Preparation of Alkyl Di( p -tolyl)sulfonium Salts and Their Application in Metal-Free C(sp 3 )-C(sp 3 ) and C(sp 3 )-C(sp 2 ) Bond Formations.

Alkyldiarylsulfonium salts were synthesized by a combination of active sulfonium species, prepared through the activation of diarylsulfoxide, and alkyl nucleophiles. The isolated sulfonium salts were subjected to the allylation and cyclopropanation of the active methylene compounds and metal-free C(sp 3 )-C(sp 2 ) couplings via oxyallyl cation intermediates under mild conditions. The series of reactions included an umpolung strategy for the coupling of alkyl nucleophiles and metal-free C-C bond formation using sulfonium salts.