Palladium-catalyzed α-arylation of sulfoxonium ylides with aryl fluorosulfates.

A variety of α-arylated sulfoxonium ylides could be facilely synthesized in modest to high yields through α-arylation of sulfoxonium ylides with aryl fluorosulfates C-O bond functionalization under palladium catalysis. 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 remained intact during the course of the reaction, and could be subjected to downstream modification.

Nickel-Catalyzed Reductive Amidation of Aryl Fluorosulfates with Isocyanates: Synthesis of Amides via C-O Bond Cleavage.

With the assistance of nickel as catalyst, 2,2'-bipyridine (bpy) as ligand, and manganese as reducing metal, the reductive amidation of isocyanates with readily accessible aryl fluorosulfates could be successfully accomplished. The reactions proceeded effectively via C-O bond activation in DMF at room temperature, enabling the facile synthesis of a range of structurally diverse amides in moderate to high yields with broad functionality compatibility. In addition, the synthetic usefulness of the method was further demonstrated by applying the reaction in scale-up synthesis and the late-stage functionalization of complex molecules with biological activities.