Electrochemical Dearomatization of Commodity Polymers

Dearomatizations are widely adopted strategies in synthetic organic chemistry that convert arenes into compounds of broader utility; however, these transformations are virtually nonexistent in macromolecular chemistry. Herein, we report the first systematic investigations into electroreductive dearomatization of common polymers, delivering polyolefinic materials without significant molecular weight changes across several orders of magnitude (103–106 Da) and with a controlled and broad range of reduction. The dearomatized and further elaborated products provided new material space that could not be obtained by using any existing polymerization or functionalization methods. This study also represents a rare example of solution-based electrosynthesis involving macromolecules and revealed an interesting electrochemical phenomenon between the molecular weight of polymer and conversion.