Controlling radical polymerization has been arguably one of the most important developments in polymer chemistry of the last few decades. The key processes, such as ATRP, NMP and RAFT, were invented by taking established small molecule chemistry but using it in a novel way — to reversibly trap growing polymer radicals as dormant species so as to minimize termination. Since their inception, intensive research has led to massive improvements in control and scope through, for example the development of ATRP catalysts with increased activity, or the development of control agents that respond to alternative stimuli such as light, electricity or pH. These developments in turn offer new opportunities in small molecule synthesis. This presentation will outline two such opportunities. First, we will show how ATRP catalysts can be used to improve Cu-based cross-coupling techniques. As part of this work, we will describe our recent efforts to increase ATRP catalyst activity, with advantages for both polymerization and synthesis. Second, we will show how alkoxyamine cleavage can be triggered electrochemically, and that this in turn can be harnessed to develop safer <i>in situ</i> on demand methylation and alkylation procedures.

Coming full circle: Adapting controlled radical polymerization for organic synthesis

ACS Spring Meeting 2021

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.