Electron Donor-Acceptor Complex-Driven Strategy Enables Initiation of Photoiniferter RAFT Polymerization from Amines, Carboxylic Acids and Alcohols

Here, we report a unified approach for photoiniferter RAFT polymerization technique allowing the utilization of organic molecules with the most ubiquitous functional groups (amines, carboxylic acids and alcohols) as initiators without significant limitations in substrate complexity and close to complete α-end functionalization. Our catalytic system relies on a combination of visible light-induced electron donor-acceptor complex-driven initiation mechanism and photocontrolled polymerization to provide polymer with controlled molar mass, low dispersity and targeted α-end functionality. Through this method, a wide range of diverse amines and carboxylic acids including biorelevant and drug-like substrates were effectively attached to polyacrylates backbone. In addition to that, we have developed a universal reagent for effective polymerization of complex amines and alcohols, which also provides a new dimension for construction of conjugates with potentially biocleavable bridge between α-end and polymer chain.