Efficient and Facile End Group Control of Living Ring-Opening Metathesis Polymers via Single Addition of Functional Cyclopropenes.

Living ROMP has become an important technique for preparing well-controlled, highly functional polymers; however, installing functional groups at the end of living ROMP polymers is not as straightforward as ROMP itself. We report a simple, efficient strategy to introduce functionalities at the chain end of living polynorbornenes via highly selective single addition of disubstituted 1,1-cyclopropenes (CPEs) with no homopropagation. Unlike many other methods for ROMP chain end functionalization, our method does not result in catalyst termination, allowing for further functionalization after CPE addition. The remarkable reactivity of such CPEs allowed for quantitative chain end functionalization to install a variety of useful functionalities, including halides, aldehydes, ketones, amines, and dyes, without using a large excess of CPEs. These polymer chain ends can be readily modified using a range of postpolymerization modifications.