Polymer-Based Adaptive Catalyst for Monoacylation of Symmetrical Diols

Although artificial catalysts have long served as a mainstay of synthetic chemistry for controlling the chemoselectivity of reactions, they often encounter an intrinsic trade-off between high selectivity and broad generality. In this study, we present a strategy to overcome this dichotomy by employing a random heteropolymer for the selective monoacylation of symmetrical diols. A single catalyst, readily prepared by radical polymerization of three monomers, exhibited exceptional monoacylation selectivity together with broad substrate adaptability, outperforming the conventional small-molecule catalysts. Mechanistic studies, together with experimental observations, suggested that a Brønsted basic monomer serves as a hydrogen- bonding anchor, positioning the diol near the reactive site and thereby facilitating the monoacylation process. This study demonstrates the untapped potential of random polymers as versatile chemoselective catalysts and paves the way for their application to a wide range of transformations.