Predominant intermolecular decarbonylative thioetherification of carboxylic acids using nickel precatalysts

Abstract

We report a general method for the direct decarbonylative thioetherification of carboxylic acids using air- and moisture-stable nickel precatalysts. In this approach, ubiquitous carboxylic acids are directly employed as aryl electrophiles and common thiols serve as sulfide donors. This protocol features excellent functional group tolerance and broad substrate scope using robust, bench- and air-stable catalysts, offering rapid entry for the synthesis of valuable aryl sulfides. The synthetic potential is showcased in the late-stage modification of pharmaceuticals directly utilizing carboxylic acid functional group. Nickel-catalyzed intermolecular decarbonylative thioetherification via C(O)–O cleavage is merged with intramolecular decarbonylation via C(O)–S cleavage, wherein thioesters are formed by thioesterification of activated carboxylic acids. Considering the significant interest in synthesis thioethers and the great utility of Ni(II) precatalysts as the privileged class of operationally-simple catalysts, we anticipate that this method will find broad applications in organic synthesis.