Novel PIB-based metathesis catalyst

ORGN 131

Hassan S. Bazzi, bazzi@tamu.edu1, Chayanant Hongfa, chongfa@mail.chem.tamu.edu2, and David E. Bergbreiter, bergbreiter@tamu.edu2. (1) Department of Chemistry, Texas A&M University at Qatar, P.O.Box 23874, Doha, Qatar, (2) Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, TX 77842-3012
Polymer supports have been extensively used in many synthetic methodologies over the last 50 years. More specifically, polymer-based catalysts have been shown to facilitate catalyst and substrate recovery. In this paper, we describe the synthesis, characterization, and applications of a modified Grubbs-Hoveyda metathesis catalyst that is covalently linked to a non-polar polyisobutylene (PIB) chain. Ruthenium metathesis catalysts have been immobilized on many insoluble supports and on water-soluble or fluorous-phase soluble polymers while retaining their catalytic activity. Our system is the first example of a soluble non-polar polymeric support. Such a support allows us to use biphasic liquid-liquid separation of the product and the catalyst. Reactions both with stoichiometric amounts of the polymer relative to Ru and in the presence of an excess of a polymer ligand allow use to regenerate and to recover the catalyst as a heptane solution. Examples will be described showing how this PIB-based catalyst can be used both in ring-closing metathesis (RCM) and ring-opening metathesis polymerization (ROMP) reactions.