Sulfate Click Chemistry

K. Barry Sharpless and his coworkers at Scripps Research Institute, in La Jolla, Calif., introduced the concept of click chemistry in the 1990s. Drawing largely on known reactions, the simple strategy involves using modular building blocks for the green synthesis of new compounds containing carbon-heteroatom linkages. Model reactions are copper-catalyzed azide-alkyne cycloadditions, which are useful in drug discovery, chemical biology research, and materials science. Sharpless and coworkers have now extended click chemistry by using SO₂F functional groups prepared from sulfuryl fluoride (SO₂F₂) to make carbon-sulfate links, for example, in the synthesis of diarylsulfates (Angew. Chem. Int. Ed. 2014, DOI: 10.1002/anie.201309399). To demonstrate a potential commercial application, Sharpless, Valery V. Fokin, and colleagues clicked together SO₂F₂, bisphenol A, and various silyl chlorides to form polysulfates, a class of tough, high-clarity polymers related to polycarbonates that has not been widely studied because the macromolecules are difficult to make (Angew. Chem. Int. Ed. 2014, DOI: 10.1002/anie.201403758).