Synthesis of (E)-chlorovinyl methylsulfanes via chlorothiomethylation of alkynes with HCl and dimethyl sulfoxide (DMSO) under metal-free and oxidant-free conditions has been reported. This methodology is rare, in which chlorovinyl methylsulfanes are constructed using chlorosulfanes rather than the combination of HCl and DMSO to react with alkynes. This procedure introduces a new application of DMSO, which is employed as a source of the SMe group to directly insert into the carbon-carbon triple bond of alkynes. Additionally, the reaction shows a broad substrate scope, good functional group compatibility, and excellent regioselectivity. Scheme 2. Scope of the substrates (All reactions are carried out on a 1.0 mmol scale, DMSO 1.0 mL, and all the listed yields are isolated yield) Scheme 3. A rational mechanism.

N-acylation of arylamines with di-and trialkyl amines has been reported. This approach provides a general synthesis of aromatic amides by an alkyl transfer through cleavage of the CÀ N bond, and acts as a model for N-dealkylations and N-acylations. Additionally, the synthesis is a promising method towards amidation reactions, wherein di-and trialkyl amine derivatives are employed as sources of acyl carbon atoms and tert-butyl hydroperoxide is employed as the oxygen source of the acyl group.