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.

Automated summary

The sulfonic acid functionalization of electron-deficient benzene sulfonic acids allows ipso nucleophilic substitution with active methylene compounds, resulting in new C-C bond formation. This method provides good to excellent yields under mild conditions without the need for transition-metal catalysts, PTC, and ligand. It offers a novel approach to incorporate various active methylene compounds into the o-nitro-substituted benzene ring and has potential applications in API synthesis and materials chemistry. The discovery of carbon-carbon bond formation by substituting a sulfonic acid group is significant.