Sustainable Pd-Catalyzed Direct Arylation of Thienyl Derivatives with (Hetero)aromatic Bromides under Air in Deep Eutectic Solvents

Abstract

An optimized protocol for the Pd-catalyzed direct arylation of 3,4-ethylenedioxythiophene (EDOT) and other substituted thiophenes with (hetero)aromatic bromides in a deep eutectic solvent made of a mixture of choline chloride/glycerol (1:2) is presented. The coupling reactions have been successfully run under air, in nonanhydrous conditions, using PdCl2 as a palladium source, with a catalyst loading as low as 1 mol %. The adjustment of each reaction component allowed finding robust conditions for the introduction of both electron-poor and electron-rich (hetero)aryl bromides with moderate-to-high yields. The sustainability of the protocol was established through calculations of green metrics, such as Eco-scale and E-factor, and compared with the literature, when possible. Remarkably, such procedure can be successfully applied for the simple preparation of conjugated organic compounds with potential applications in optoelectronics, as we have shown, by obtaining two molecules previously reported as a hole transport material for perovskite solar cells and the final intermediate of a photosensitizer for dye-sensitized solar cells.