DMSO-DCE Triggered Chemodivergent C-Methylenation of Electron-Rich Arenes: An Easy Access to Diarylmethanes.

The chemodivergent property of dimethyl sulfoxide (DMSO) along with 1,2-dichloroethane (DCE) was exploited for the incorporation of a methylene group to form diarylmethanes through a dearomatization/rearomatization process. Methyl(methylene)sulfonium ions (CH2=S+-Me) were generated by simple heating of commonly used solvents such as DMSO and DCE. These ions were subsequently trapped by electron-rich arenes and heteroarenes, resulting in the synthesis of both symmetrical and unsymmetrical diarylmethanes. This protocol was further extended to access N-methylenamides by reacting 2-naphthol with amides or nitriles in the presence of DMSO and DCE.

Metal-Free C-H Sulfamidation of 1,4-Naphthoquinone in Water.

Direct sulfamidation of 1,4-naphthoquinones using N-methoxy sulfonamides under metal-free conditions in water was developed. Base-mediated nucleophilic addition of N-methoxy sulfonamides, followed by N-O bond cleavage allowed the formation of enesulfonamides. Further, the synthesis of pyrrolonaphthoquinones proved the practicability of the current approach.