Owing to the global scale establishment of polymer technology in the past few generations, the capability to carry out new polymerization reactions typically affords new applications and processes with far reaching implications. Here, we report a novel polymerization methodology utilizing homogenous gold catalysis (HGC) to facilitate the reaction of an unsaturated substrate with a dialkyne. Through optimization of the catalyst, ligand, solvent, and reaction parameters these polymerizations have been demonstrated to yield high molecular weight products under facile reaction conditions. Additionally, the unique 1,1-alkenyl linkage formed through the process gives rise to novel polymer architectures and connectivities. The high functionality tolerance of HGC allows for incorporation of diverse functionalities into the synthesized polymer system, affording large increases in structural complexity starting from simple substrates. Through an extensive investigation of unsaturated substrates and dialkynes with varying steric bulk, electron density, and substitution patterns, we have demonstrated a modular synthetic approach toward accessing novel polymer architectures derived from unsaturated substrates.

Gold catalyzed polymerization reactions of unsaturated substrates: Toward new macromolecular chemistries

2019 Spring National Meeting

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