Nickel-Catalyzed Negishi-Type Arylation of Trialkylsulfonium Salts

Negishi-type arylation of trialkylsulfonium salts with arylzinc reagents has been accomplished under nickel catalysis. The use of cyclohexanethiol as an additional ligand was found to be particularly important to promote C-S cleavage. The present reaction accommodates one-pot arylation of dialkyl sulfides by combining with S-methylation with MeOTf. Mechanistic experiments suggest that C-S cleavage would proceed via single-electron transfer (SET) to generate the most stable carbon-centered radical and that the thiolate ligand would promote the C-S cleavage and radical recombination step.

Automated summary

The Negishi-type arylation of trialkylsulfonium salts with arylzinc reagents has been achieved under nickel catalysis. The use of cyclohexanethiol as an additional ligand was found to be crucial for promoting C-S cleavage. Mechanistic experiments suggest that the reaction proceeds through single-electron transfer to generate a stable carbon-centered radical, with the thiolate ligand facilitating C-S cleavage and radical recombination.