Vinylic Addition Polynorbornene in Catalysis

Abstract

Vinylic addition polynorbornenes (VA-PNB) result from the insertion polymerization of norbornene or specific norbornene derivatives catalyzed by transition metal com- plexes. The VA-PNB skeleton is completely aliphatic and keeps the bicyclic structure of norbornene. This saturated polymer is thermally and chemically very stable and it is a very robust scaffold to support catalysts or reagents for catalytic applications. Several VA-PNBs are now available with suitable functional groups (halogen, alkenyl, carbonates) that can be used as starting materials to introduce the functionalization of choice by post-polymerization reactions. This has been applied to anchor organocatalysts on VA-PNB as well as ligands that can be used to synthesize supported metal catalysts. The reported examples of the use of VA-PNB-linked catalysts and their recyclability will be presented. VA-PNBs have also proved useful in the context of organotin chemistry to solve the problem of tin contamination by an efficient separation and the reuse of tin byproducts. Its uses in the Stille cross-coupling reaction and tin-hydride radical proc- esses will be discussed.