Oxidation of Alkylcatecholboranes with Functionalized Nitroxides for Chemical Modification of Cyclohexene, Perallylated Polyglycerol and of Poly(butadiene)

Wagner CB, Studer A

Abstract

The present communication reports on the synthesis of alkoxyamines by hydroboration of olefins with catecholborane and subsequent oxidation by using nitroxides. Oxidation occurs via a radical process and the intermediately formed Cradicals are trapped by the nitroxides to form the corresponding alkoxyamines. If functionalized nitroxides are used, the method allows incorporation of interesting functional moieties via this approach. The novel method is applied for chemical modification of cyclohexene as a test substrate. More importantly, it is also shown that the reaction sequence can be used for chemical modification of macromolecules containing multiple double bonds. This is documented by successful functionalization of poly(butadiene) and of perallylated polyglycerol.