A variety of α-arylated sulfoxonium ylides could be facilely synthesized in modest to high yields through an α-arylation of sulfoxonium ylides with aryl fluorosulfates via C-O bond cleavage under palladium catalysis. The reactions using readily available and bench-stable aryl fluorosulfates as effective and appealing arylating agents showed both good substrate scope and broad functionality tolerance. Important functional groups such as nitro, cyano, formyl, acetyl, methoxycarbonyl, trifluoromethoxy, fluoro, and chloro embedded in substrates kept intact during the course of the reaction, which could be subjected to downstream modification. In addition, the reaction could be readily scalable and be applied in the late-stage modification of complex molecule.

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