Polymacrocycles Derived via Ugi Multi‐Component Reactions

: The synthesis of macrocycles based on the Ugi-4CR has been thoroughly explored by Wessjohann and coworkers, while polymerizations utilizing the Ugi-4CR are already patented by Ugi and recently studied more in detail, developing a new trend in polymer chemistry. Here, the combination of both, that is, the synthesis of polymacrocycles, is demonstrated. As diverse functional groups can be easily introduced in a macrocycle via Ugi-4CR, a straightforward design of polymacrocycles is achieved in a two-step procedure. First, the Ugi-4CR of 10-undecenoic acid, a diamine, a diisocyanide, and an aldehyde results in diversely substituted macrocycles having two terminal double bonds. Subsequently, these macrocycles are polymerized by ADMET (acyclic diene metathesis) or thiol-ene polymerization to generate polymacrocycles with potential application in coordination chemistry as, for example, sensors, filters, or phase-transfer catalysts. Moreover, the setup of the literature-known Ugi macrocyclization is simplified by systematic reaction screening.