C-H Activation of Functional Materials

Abstract

This thesis comprises three projects on the theme of C-H activation for the synthesis of functional materials. Chapter 1 describes the development of gamma C-H carbonylation of free aliphatic secondary amines to form secondary lactams. The diastereoselectivity of the reaction was found to be significantly influenced by the choice of reaction conditions. Under optimised conditions, a wide range of lactams were delivered in high yields and good d.r., with many different functional groups and substitution patterns being tolerated. Further transformation of the lactam was also demonstrated, yielding pyrrolidines and functionalised lactams. Chapter 2 describes the development of a carboxylate directed C-H arylation of azulene at the 2-position. This methodology enables the overriding of the natural reactivity of the 1, 3-position to conveniently access 2-arylated azulene, without regioselectivity issues and in moderate to high yields. The reaction was found to tolerate a wide range of aryl groups, including some heteroarenes. In-situ decarboxylation was also observed, allowing the carboxylate to act as a traceless directing group. This methodology was subsequently applied to the preparation of 2-functionalised azulene – fluorene polymers in chapter 3. These polymers were then tested for electrochromic applications and optical sensitivity to acidic environment. Functionalisation of azulene was found to significantly influence the properties of these polymers. In particular, electron-donating aryl groups were found to enhance the sensitivity of the polymers to acidic environments.