Highly Functionalized SuFEx-able Hub Bearing All-Carbon Quaternary Center via Rapid Brønsted Superbase Catalysis

A rapid Brønsted superbase catalysis for highly functionalized sulfur­(VI)–fluoride exchange (SuFEx) hubs bearing all-carbon quaternary centers was developed. Remarkable functional group tolerance toward esters and nitriles was achieved by Michael addition of cyanoacetate derivatives to ethenesulfonyl fluoride with low catalyst loadings (∼0.5 mol %) within a short reaction time (0.5–30 min). Gram-scalability, water tolerance, and compatibility in polymeric catalysis showcase its unique practicability. SuFEx click conjugations were demonstrated using various amines, including DNA-tethered biomolecules.