Electroediting of Soft Polymer Backbones

Abstract

Synthetic methods that edit soft polymer backbones are critical technologies for tailoring the structures and properties of macromolecules. Developing strategies that leverage underexplored reaction manifolds are vital for accessing new chemical (and functional) space in soft materials. Here, we report a mild electrochemical approach that enables both degradation and functionalization of synthetic polymers. We found that bulk electrolysis (under either homogeneous or heterogeneous conditions) promoted facile, chemoselective chain scission in a variety of olefin-containing materials. Polymer degradation could also be coupled with functionalization (e.g., azidation) to afford new species that could serve as macromonomers.

Electrochemical Late-Stage Functionalization

“…Yoshida introduced the concepts of electroauxiliaries and cation pool to increase the electrosynthesis viability in the late 20th century. − Meanwhile, Steckhan elegantly formalized the principles of indirect electrolysis, which thereafter brought forth numerous mediator-driven processes. , Subsequent key achievements on the direct electrolysis were made by Schäfer, Lund, Little, − Moeller, Jutand, and Amatore around the 21st century. On the basis of these pioneering contributions, electro-organic synthesis reemerged in the past decade, with major contributions by Baran, Xu, Lei, Ackermann, Lambert, Lin, Gouin, Waldvogel, Stahl, Malins, and Mei, among others. − Thus, major advances have been achieved in various fields, including C–H activation, reductive cross-electrophile coupling, alkene difunctionalization, nitrogen-centered radical mediated chemistry, total synthesis, and the LSF of natural products and medicinally relevant molecules (Scheme b).…”

Electrochemical Syntheses of Polycyclic Aromatic Hydrocarbons (PAHs)

“…[25][26][27][28][29][30][31][32][33][34][35] In terms of material chemistry, the electro-oxidated aromatic couplings proved efficient to prepare 𝜋-extended molecules, [36][37][38] and the electrochemical tools have also been exploited for the synthesis of polymers, [39][40][41][42] energetic compounds, [43] as well as the late-stage diversification of materials. [44][45][46] Likewise, electrochemistry provided new avenues for PAHs synthesis and gained considerable momentum by both direct electrolysis and mediated electrolysis (Figure 1).…”

Upcycling of Polybutadiene Facilitated by Selenium‐Mediated Allylic Amination

“…[12][13][14][15] Recently, strategies for the functionalization of polystyrene, [16] polyolefins, [17][18][19][20] polyethers, [21] polylactides, [22] and polyacrylates [23,24] have evolved concurrently with the modernization of synthetic organic methodology. [25] Advances in CÀ H activation, [8] (photo)redox catalysis, [21,26,27] and organocatalysis [17,18] have enabled the streamlined synthesis of previously inaccessible macromolecules from post-con-sumer plastics. On the other hand, fewer examples exist for the direct upcycling of unsaturated rubbers (e.g., polybutadiene, polyisoprene), the main constituents in consumer tires.…”