Eugenol‐Derived Sustainable Cyclic Carbonates and Polythiocarbonates from CO ₂ and COS as Efficient Hybrid Catalysts for Suzuki–Miyaura Cross‐Coupling Reactions

ABSTRACT Currently, the increasing demand for sustainable and degradable polymers from resources that reduce the reliance on petroleum‐based materials is receiving much attention. This transition is driven by the unchecked and persistent accumulation of non‐biodegradable wastes in the ecosystem. Herein, a novel palladium‐ligated polymer catalyst was prepared via the copolymerization of COS and eugenol‐based bio‐epoxide. The property of the copolymer was greatly enhanced by post‐polymerization modification via alkyne‐azide click chemistry, followed by effective incorporation of palladium (Pd) in the polymeric chain. Copolymerization was catalysed by binary catalytic systems comprising (salen)CrX or (salophen)CrX in combination with onium salts to afford poly(monothiocarbonate)s with good yield. The chemical composition and structures of resulting materials were characterized by spectroscopic techniques like FTIR, 1 H NMR and ESI‐MS. The synthesized polymer was subsequently evaluated as a hybrid catalyst for Suzuki cross‐coupling reactions, exhibiting high catalytic efficiency at lower catalyst loadings and excellent recyclability with negligible loss of catalytic activity. A corresponding Pd complex containing a cyclic carbonate ligand was also synthesized to compare its catalytic activity with the polymeric catalyst, which shows comparatively less activity and no recyclability. Hence, this work presents a method for fabricating a highly active bio‐based polymeric catalyst and expanding the scope of green chemistry.