Unprecedented C-C Bond Formation via Ipso Nucleophilic Substitution of 2,4-Dinitrobenzene Sulfonic Acid with Active Methylene Compounds.

The sulfonic acid functionalization of sufficiently electron-deficient benzene sulfonic acids undergoes ipso nucleophilic substitution with various active methylene compounds, leading to new C-C bond formation. Good to excellent yields are obtained under mild conditions without transition-metal (Pd or Cu) catalyst, PTC, and ligand. No solid waste is generated. It is a highly effective strategy for incorporating various active methylene compounds into the o- nitro-substituted benzene ring. This method has been applied not only for synthesizing APIs but also in materials chemistry. It shows a novel route for creating heavily crowded all-carbon quaternary centers. Carbon-carbon bond formation by substituting a sulfonic acid group was unknown.