Utility of a heterogeneous palladium catalyst for the synthesis of a molecular semiconductor via Stille, Suzuki, and direct heteroarylation cross-coupling reactions

Abstract

The commercially available silica-supported heterogeneous catalyst SiliaCat® DPP-Pd has proven to be highly active, robust, and reusable for the synthesis of a thiophene–phthalimide-based molecular semiconductor under microwave-irradiation reaction conditions. A Stille reaction protocol demonstrated that SiliaCat® DPP-Pd outperformed well-known homogeneous catalysts, Pd(PPh₃)₄ and Pd(PPh₃)₂Cl₂, in terms of performance and catalyst loading, while also exhibiting tolerance to ambient reaction conditions and two-fold recyclability for the formation of product. The success established for SiliaCat® DPP-Pd catalyzed Stille reactions via microwave irradiation was extended to optimize Suzuki coupling and direct heteroarylation protocols. Notably, direct heteroarylation with SiliaCat® DPP-Pd exhibited excellent selectivity and perturbed the formation of homo-coupled aryl bromides, two side reactions that are known to plague this type of cross-coupling reaction.