C-SuFEx Linkage of Sulfonimidoyl Fluorides and Organotrifluoroborates

Abstract Sulfur(VI) fluoride exchange (SuFEx), a new type of linkage reaction, has excellent potential for application in functional molecule linkage to prepare pharmaceuticals, biomolecules, and polymers. Herein, a C-SuFEx catalytic reaction was established to achieve fast (in minutes) linkage between sulfonimidoyl fluorides and aryl/alkyl organotrifluoroborates. Potassium organotrifluoroborates were instantaneously activated via trimethylsilyl triflate to afford organodifluoroboranes, releasing BF3 as a catalyst in situ. This C-SuFEx technique was capable of forming S(VI)-C(alkyl), S(VI)-C(alkenyl) and S(VI)-C(aryl) bonds, demonstrating its broad scope and thus surpassing the achievements of previous studies. Natural products and pharmaceuticals with sensitive functional groups, such as valdecoxib, celecoxib and diacetonefructose, are compatible with this protocol, allowing the formation of diverse sulfoximines.