ADMET Synthesis of Polyolefins Targeted for Biological Applications

A series of “ N-terminus ” amino acid and peptide branched, chiral polyolefins, termed bio-olefins, have been prepared using acyclic diene metathesis (ADMET) polycondensation chemistry, using a minimal amount of solvent and Grubbs' second generation catalyst. The carboxylic acid functional groups were protected with methyl, benzyl, and tert -butyl esters to enhance both the polymerizability of the monomers themselves and the solubility of the resulting polymers. A number of these polymers are semicrystalline, exhibiting melt transitions of up to 132 and 74 °C for the amino acid and dipeptide branched polymers, respectively. Adding a succinic acid spacer between the amino acid entity and the polymer backbone alters the melting behavior of the polymer, increasing the peak melting point by 27 °C when compared to a polymer having the same amino acid directly attached to the polymer backbone.