Direct 1,2-oxosulfenylation of acetylenic sulfones with dimethyl sulfoxide (DMSO) is realized under microwave irradiation. The current method provides a direct and efficient route to synthesize β-keto thiosulfones from acetylenic sulfones and DMSO, featuring metal-free, low cost, and convenient advantages. The mechanistic investigations in-dicate that acetylenic sulfones first react with DMSO to generate sulfonium ylides through the nucleophilic addition, cyclization, and 4e ring opening. The sulfonium ylides and the DMSO-generated dimethyl sulfide at the aid of the ylides undergo a radical process to form β-keto thiosulfones under heating.

N-(2,2-Diphenylvinyl)-β-oxoamides are both the structural moiety of biologically active compounds and important synthetic intermediates. Structurally diverse N-(2,2-diphenylvinyl)-β-oxoamides are prepared efficiently from 2-diazo-1,3-dicarbonyl compounds and N-alkyl-2,2-diphenylaziridines via an electrophilic ring opening...

A phenyltrimethylammonium tribromide-mediated nucleophilic substitution/oxygen transformation reaction of benzyl halides with DMSO has been developed. In this transition-metal-free reaction, DMSO acts as not only a solvent but also a “S­(O)­Me” source, thus providing a convenient method for the efficient and direct synthesis of various benzyl methyl sulfoxides.

Bifunctionalized sulfonium ylides, sulfonium acyl sulfonyl methylides, were directly and efficiently prepared from various acetylenic sulfones and aliphatic sulfoxides under heating conditions. The current method features short reaction time, low cost, readily available starting materials, convenient operation and purification, providing an efficient access to widely applied bifunctionalized sulfonium ylides.

Microwave-assisted direct oxidation of N-arylethynylsulfonamides with DMSO as a nucleophilic oxidant and solvent affords N-sulfonyl-2-aryloxoacetamides without any other additional electrophilic activators or oxidants.