Polymer modification is one of the fundamental pillars of polymer chemistry because it grants the practitioner access to a broad scope of materials properties from a small number of polymer scaffolds. Thus far, the central paradigm of polymer modification has been to alter the composition of the polymer periphery—e.g., installation of side-chains—which limits the magnitude and variety of possible changes in polymer properties. In contrast, transforming the composition of the polymer backbone itself has, by and large, gone neglected; yet, the ability to carry out such modification would impart global changes to materials properties on demand. In this talk, I will describe our work on sigmatropic rearrangements of polymer backbones. More than a century since the first report of a sigmatropic rearrangement in 1912, and a plethora of applications in the context of "small" molecules, only ten studies have explored sigmatropic rearrangements in the context of polymers: five of these studies were theoretical, and the rest—peripheral modifications. Our work demonstrates that these powerful concerted rearrangements can, under mild conditions, induce a polymer chain to undergo a metamorphosis from one class of polymers to another, which leads to dramatic changes in polymer properties. Beyond stimulus response, such polymer backbone modification can grant entry to previously inaccessible scaffolds. More broadly, our work advances the sophistication of retrosynthetic analysis applied to polymers.

Sigmatropic rearrangements of polymer backbones

ACS Fall 2021

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