Regio- and Stereoselective Ring-Opening Metathesis Polymerization of 3-Substituted Cyclooctenes

J. Am. Chem. Soc., 2011, 133 (15), pp 5794–5797

Regio- and Stereoselective Ring-Opening Metathesis Polymerization of 3-Substituted Cyclooctenes

Shingo Kobayashi, Louis M. Pitet, and Marc A. Hillmyer*

hillmyer@umn.edu

Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States

3-Substituted cis-cyclooctenes (3RCOEs, R = methyl, ethyl, hexyl, and phenyl) were synthesized and polymerized, and the polymers therefrom were hydrogenated to prepare model linear low density polyethylene (LLDPE) samples.

Ring-opening metathesis polymerization (ROMP) of the 3RCOEs using Grubbs' catalyst proceeded in a regio- and stereoselective manner to afford polyoctenamers [poly(3RCOE)] exhibiting remarkably high head-to-tail regioregularity and high trans-stereoregularity. Overall selectivity increases with the increasing size of the R substituent. Hydrogenation of poly(3RCOE)s affords precision LLDPEs with R substituents on every eighth backbone carbon.

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