Efficient Transformation of Polymer Main Chain Catalyzed by Macrocycle Metal Complexes via Pseudorotaxane Intermediate

Post‐synthesis modification of polymers streamlines the synthesis of functionalized polymers, but is often incomplete due to the negative polymer effects. Developing efficient polymer reactions in artificial systems thus represents a long‐standing objective in the fields of polymer and material science. Here, we show unprecedented macrocycle‐metal‐complex‐catalyzed systems for efficient polymer reaction that result in 100 % transformation of the main chain functional groups presumably via a processive mode reaction. The complete polymer reactions were confirmed in not only intramolecular reaction (hydroamination) but also intermolecular reaction (hydrosilylation) by using Pd‐ and Pt‐macrocycle‐catalyzed systems. The most fascinating feature of the both reactions is that higher‐molecular‐weight polymers reach completion faster. Various studies suggested that the reactions occur in the catalyst cavity via the formation of a supramolecular complex between the macrocycle catalyst and polymer substrate like pseudorotaxane, which should be of characteristic of the efficient polymer reactions progressing in a processive mode. Post‐synthesis modification of polymers streamlines the synthesis of functionalized polymers, but is often incomplete due to the negative polymer effect. Here, we show macrocycle‐metal‐complex‐catalyzed systems for efficient transformation of main chain in polymer substrate, whereby higher‐molecular‐weight polymers reach completion faster. Mechanistic studies suggest the reactions proceed via the formation of a pseudorotaxane intermediate.