cis-Selective Acyclic Diene Metathesis Polymerization of ,-Dienes. Academic Article uri icon

abstract

  • The cis/trans stereochemistry of repeating alkenes in polymers provides a powerful handle to modulate the thermal and mechanical properties of these soft materials, but synthetic methods to precisely dictate this parameter remain scarce. We report herein a cis-selective acyclic diene metathesis (ADMET) polymerization of readily available ,-diene monomers with high functional group tolerance. Identification of a highly stereoselective cyclometalated Ru catalyst allowed the synthesis of a broad array of polymers with cis contents up to 99%. This platform was leveraged to study the impact of the cis geometry on the thermal and mechanical properties of polyalkenamers, including an ABA triblock copolymer synthesized via extension of a cis-rich telechelic polyoctenamer with d,l-lactide. These results suggest that cis-selective ADMET affords an efficient strategy to tune the properties of a variety of polymers.

published proceedings

  • J Am Chem Soc

author list (cited authors)

  • Kempel, S. J., Hsu, T., Nicholson, J. L., & Michaudel, Q.

complete list of authors

  • Kempel, Samuel J||Hsu, Ting-Wei||Nicholson, Jake L||Michaudel, Quentin

publication date

  • June 2023