Twisted amides are a special class of molecules that have distorted, non-planar amide bonds due to the geometric constraints imposed by a bicyclic framework. As a result of this twist, the amide nitrogen becomes very nucleophilic and the carbonyl group becomes more electrophilic. While these reactive molecules have long been studied in physical organic chemistry, their potential as monomers for ring-opening polymerization has remained unexplored. Here, we demonstrate the potential of twisted amides to polymerize through a new mechanism for controlled, living polymerization termed “halide rebound polymerization.” Initiated by simple alkyl halides, the polymerization of twisted amides is a unique case of covalent electrophilic polymerization that produces polymers with living chain ends that are stable to ambient conditions. This permits the isolation of the polymer followed by chain extension to produce block polymers. The resulting polymers are thermally stable and have high glass transition temperatures. By modifying the twisted amide structure, the rates of polymerization can be tuned and predicted through computational analysis.

Halide rebound polymerization of twisted amides

2019 Spring National Meeting

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