Construction of N–S and C–N Bonds from Reactions of Benzofuroxans with DMSO or THF

[Image: see text] Novel ring-opening reactions are achieved employing benzofuroxan as a new type of iminating or aminating reagent. These diverse transformations give access to three types of molecular scaffolds, N-aryl dimethylsulfoximines, methanesulfonamides, and hemiaminal ethers, which are important structural motifs in organic and medicinal chemistry. The procedures feature solvent-involved reactions, easily available starting materials, operational simplicity, high atom economy, and the potential further transformation of nitro group.