Biomimetic Carbocationic Polymerizations Iv: Carbocationic Polymerization of Isoprene Initiated by Dimethyl Allyl Alcohol

In this article, we investigate a new bio-inspired synthetic route towards NR homologs based on the carbocationic polymerization of isoprene initiated by dimethyl allyl alcohol (DMAOH)/TiCl4 or BF3.Et2O as the catalytic system. This study is the continuation of our studies related to the proof of principle that NR biosynthesis is based on a carbocationic mechanism. It is shown that using the biomimetic strategy of initiation by allylic carbocations, polyisoprene carrying a dimethyl allyl head group is produced almost exclusively via 1,4 addition, yielding repeating units with cis and trans configurations. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2181–2189, 200