The development and application of a novel endo furan-protected maleimide building block is reported. The endo isomer undergoes deprotection at temperatures ∼50 °C below the exo derivative. This enables a simple and powerful approach to quantitatively and selectively introduce functional maleimide groups via temperature modulation.

A novel method for facile postpolymerization functionalization of synthetic polymers using terminal norbornadiene (NBD) building blocks is presented. Incorporation of the NBD functionality streamlines the synthesis of a wide array of block polymers utilizing multistep click chemistry strategies. Previously, the use of NBD-functionalized initiators produced polymers that underwent a cascade of Diels-Alder (DA) reactions to unveil a reactive cyclopentadiene (Cp) chain end. When coupled with a maleimide-bearing counterpart, a highly efficient DA cycloaddition with the terminal Cp can occur. To extend this concept to a range of polyacrylates and commercially available poly(ethylene glycol) systems, we developed a novel NBD acid building block for postpolymerization functionalization. Employing this process, we have demonstrated straightforward access to a library of block polymers that leverage this NBD click platform.

Herein, we report the development of a scalable and synthetically robust building block based on norbornadiene (NBD) that can be broadly incorporated into a variety of macromolecular architectures using traditional living polymerization techniques. By taking advantage of a selective and rapid deprotection with tetrazine, highly reactive "masked" cyclopentadiene (Cp) functionalities can be introduced into synthetic polymers as chain-end groups in a quantitative and efficient manner. The orthogonality of this platform further enables a cascade "click" process where the "unmasked" Cp can rapidly react with dienophiles, such as maleimides, through a conventional Diels-Alder reaction. Coupling proceeds with quantitative conversions allowing high molecular weight star and dendritic block copolymers to be prepared in a single step under ambient conditions.