Document Type

Theses, Ph.D


Available under a Creative Commons Attribution Non-Commercial Share Alike 4.0 International Licence

Publication Details

A thesis presented to Technological University Dublin for the award of Doctor of Philosophy, February 2016.


This work concerns the preparation of novel [2.2]paracyclophane derivatives intended for use as asymmetric ligands and investigations into surface coatings prepared from [2.2]paracylophanes. This begins with a general introduction to enantioselective synthesis, followed by a review of relevant reported ligands based on the [2.2]paracyclophane framework and their applications. Next is described the preparation of novel ligands based on the [2.2]paracyclophane structure. Starting with the preparation of a range of mono and disubstituted [2.2]paracyclophanes, including several novel analogues, this moves on to investigating resolution procedures where a novel method for the preparation of enantiopure 4-bromo[2.2]paracyclophane is described. The coupling of prepared phenyl oxazoline analogues with the [2.2]paracyclophane moiety via the Buchwald-Hartwig amination is used to prepare several novel ligands and characterisation, along with a detailed investigation in the optimisation of their synthesis is presented. The focus of the work then moves to the analogous octafluoro[2.2]paracyclophane and several routes towards its preparation are investigated. The structure was functionalised and attempts at preparing analogous fluorinated ligands to those already detailed are discussed. Protective surface coatings prepared from [2.2]paracyclophanes are known as parylenes and herein is presented methods for improved surface adhesion of these coatings. This was accomplished through the use of sol-gel coating pre-treatments. The pre-treatment formulations presented were characterised and ultimately proved superior to the current industrial benchmark. A number of fluorinated sol-gel additives were also prepared and characterised, two of which are novel, along with a brief study on the incorporation of organic dyes into sol-gel coatings.