Synthesis of Differentiated Sulfur-Containing Polymers by Regiodivergent Polymerization of Morita-Baylis-Hillman Acetates and Thiols

The development of facile strategies to access differentiated functional polymers starting from identical monomers is challenging yet desirable in polymer chemistry. Herein, we report a novel regiodivergent polymerization strategy for synthesizing differentiated sulfur-containing polymers starting from Morita-Baylis-Hillman (MBH) acetates and thiols. By properly selecting the catalysts and reaction conditions, the polymerization could be performed efficiently with a range of MBH acetates and thiols under ambient conditions, allowing access to differentiated sulfur-containing polymers with excellent alpha- or gamma-regioselectivity. Meanwhile, density functional theory calculations were used to elucidate the origin of the regioselectivity of the polymerizations. In addition, the resulting alpha- and gamma-polymers possessed different glass transition temperatures and refractive index values, and the gamma-polymers could be transformed into the corresponding alpha-polymers under radical conditions. This work represents a new strategy to synthesize structurally diverse functional polymers with tailored properties.