Diverse reactivity of maleimides in polymer science and beyond

Maleimides are remarkably versatile functional groups, capable of participating in homo- and copolymerizations, Diels-Alder and (photo)cycloadditions, Michael additions, and other reactions. Their reactivity has afforded materials ranging from polyimides with high upper service temperatures to hydrogels for regenerative medicine applications. Moreover, maleimides have proven to be an enabling chemistry for pharmaceutical development and bioconjugation via straightforward modification of cysteine residues. To exert spatiotemporal control over reactions with maleimides, multiple approaches have been developed to photocage nucleophiles, dienes, and dipoles. Additionally, further substitution of the maleimide alkene (e.g., mono- and di-halo-, thio-, amino-, and methyl-maleimides, among other substituents) confers tunable reactivity and dynamicity, as well as responsive mechanical and optical properties. In this mini-review, we highlight the diverse functionality of maleimides, underscoring their notable impact in polymer science. This moiety and related heterocycles will play an important role in future innovations in chemistry, biomedical, and materials research.