Cyclopentadienes (Cp) have a multitude of synthetic applications due to their electron-rich and conformationally-locked dienes. This makes them an ideal diene in Diels–Alder reactions for conjugation chemistry and the synthesis of natural products. However, due to its high reactivity, cyclopentadiene is unstable and can dimerize or undergo an acid-catalyzed polymerization. Despite the potential of Cp for conjugation chemistry, its incorporation into polymers has been limited to end-chain modification. The synthesis of Cp-containing monomers for ATRP or RAFT polymerizations is challenging because of the rapid Diels–Alder cyclization that occurs with the vinyl functionality of the monomers. To circumvent this issue, we report the use of a protecting group on the Cp that is stable to RAFT polymerization conditions and can be easily removed after polymer isolation. The deprotection of Cp and a subsequent Diels–Alder reaction can be done in one step, forming diblock or brush copolymers. To highlight this new approach, a series of post-polymerization reactions will be described to access new functional materials.

Selective deprotection of cyclopentadiene as a platform for functional polymeric materials

255th National Meeting (2018)

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