Sulfur-containing polymers, such as thioesters and thiocarbonates, offer sustainability advantages, including enhanced degradability and chemical recyclability. However, their synthesis remains underdeveloped compared to that of their oxygen-containing counterparts. Although catalytic ring-opening copolymerization (ROCOP) can provide access to sulfur-containing polymers, these materials often exhibit uncontrolled microstructures and unpredictable properties. A comprehensive model that elucidates the factors determining selectivity in these catalytic reactions is still lacking, despite its central importance for advancing these polymerizations into widely applicable methodologies. In this study, we investigate the factors that lead to selectivity in sulfurated ROCOP across various monomer combinations, including thioanhydrides or carbon disulfide with epoxides, thiiranes, and oxetanes. We find that unwanted by-products primarily arise from backbiting reactions of catalyst-bound alkoxide chain ends, which can be mitigated by (i) selecting monomers that form primary alkoxide of thiolate chain ends, (ii) maximizing ring strain in the backbiting step, and (iii) timely termination of the polymerization. By applying these strategies, the selectivity of the catalytic ROCOP can be controlled and we successfully synthesized perfectly alternating poly(esters- alt -thioesters) from various oxetanes and the highly industrially relevant ethylene oxide. Our study thereby shifts the focus for achieving selectivity from catalyst to monomer choice providing valuable mechanistic insights for the development of future selective polymerizations, paving the way for sulfurated polymers as potential alternatives to current commodity materials.
