Alkyl-substituted trithiocarbonates enable performing open-to-air RAFT polymerization regardless of the presence or absence of an R-group†
Abstract
The development of fully oxygen-tolerant reversible addition–fragmentation chain transfer (RAFT) polymerization is a challenge in synthetic chemistry. Herein, symmetrical bis-(ethanesulfanylthiocarbonyl) disulfide (BisESD) and bis(propylsulfanylthiocarbonyl) disulfide (BisPSD) are successfully utilized to produce well-defined polymers without loss of the living polymerization feature under fully open conditions. A persistent trithiocarbonate (TTC) radical capable of initiating polymerization is a key element for open-to-air RAFT polymerization. Furthermore, with the assistance of high-throughput (HTP) screening, we found that alkyl-substituted trithiocarbonates possess the ability to perform fully oxygen-tolerant RAFT polymerization regardless of the presence or absence of an R-group. We firmly believe that oxygen-tolerant trithiocarbonate radical initiation will become a versatile strategy for fully oxygen-tolerant RAFT polymerization.