Synthesis of polycyclic aromatic hydrocarbon containing cyclophanes: new and improved methodologies

MacKinnon, Marc Richard (2020) Synthesis of polycyclic aromatic hydrocarbon containing cyclophanes: new and improved methodologies. Doctoral (PhD) thesis, Memorial University of Newfoundland.

[English] PDF - Accepted Version Available under License - The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission. Download (14MB)

Abstract

Cyclophanes are a vast class of compounds that can be defined as any system containing an aromatic system bridged by at least one n-membered bridge (n≥0). This description encompasses a large number of compounds, but relatively few examples in which the aromatic system is more complex than benzene exist. This is largely due to the increase is synthetic difficulty and a lack of universal methodologies. The work described in this thesis includes improvements in the synthesis of pyrenophanes and the introduction of new methodology for cyclophane formation in which the aromatic unit is peropyrene. Chapter 1 serves as an introduction to the concept of non-planarity in aromatic systems and the strategies for incorporating such morphologies into structures. Focus has been placed primarily on cyclophanes containing one aromatic system and one bridge and their advantages in structural modulation. Chapter 2 contains a review of the history of pyrenophanes and strategies towards their preparation. Improvements to the synthesis of the 1,n-dioxa-[n](2,7)pyrenophanes and [n](2,7)pyrenophanes are discussed in detail. Additionally, the reactivity of these systems is briefly discussed. Chapter 3 introduces peropyrene and discusses its properties and limited synthetic accessibility. The synthesis of a series of new cyclophanes is discussed which takes advantage of the dimerization of phenalenlyl radicals generated phenalene. Characterization of resulting [n](2,6)peropyrenophanes is briefly discussed.

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