An 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 the 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 providing close to complete α-end functionalization of synthesized polymers. Our catalytic system relies on a combination of visible light-induced electron donor-acceptor complex-driven initiation mechanism and photocontrolled radical polymerization to provide polymers 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 polyacrylate backbone. In addition to that, we have developed a reagent for effective initiation from complex amines and alcohols, which also provides a new dimension for the construction of conjugates with potentially biocleavable bridge between the α-end and polymer chain.