Palladium-Catalyzed Hiyama Cross-Coupling of Aryl Fluorosulfates

We report an efficient, practical, and scalable approach for the palladium-catalyzed Hiyama-type coupling of (hetero)arylsilanes with aryl fluorosulfates (aryl-OFs) as competent electrophiles via C-O bond activation. This protocol features an exceedingly broad scope, remarkable functionality compatibility, and exquisite reactivity (OFs over OTf, OTs, OMs, and ONs), which could be performed in one pot from phenolic raw materials without isolation. The late-stage modification of pharmaceutically relevant, drug-like molecules and tyrosine-containing peptides enhanced the enabling utility of this methodology.