Solvent‐free, B(C6F5)3‐Catalyzed S−H Insertion of Thiophenols and Thiols with α‐Diazoesters

-catalyzed S-H insertion reaction of thiophenols and thiols with α-diazoesters to access valuable α-thioesters. With the established protocol, an array of α-thioester products are generated in moderate to good yields with broad scope and functional group tolerance. In addition, this reaction maintains its high efficiency on gram scale and the product can be easily transformed into other useful motifs. This reaction proceeds under solvent-free conditions at room temperature, and generally finishes in twenty minutes upon magnet stirring, which offers an expedient way for the synthesis of thioether-containing compounds.