The discovery and investigation of novel rearrangements of cyclobutenediones triggered by nucleophilic addition

Abstract

This thesis entails the discovery and investigation of two new modes of cyclobutenedione rearrangement. The rearrangement of cyclobutenones has been well established in the past and has proven to be a robust method for the synthesis of a wide variety of substrates e.g. quinones and furanones. This has also been extended to the synthesis of a number of natural products and biologically active compounds. Despite this, the rearrangement of cyclobutenediones is less prominent. Herein is described two new modes of this class of rearrangements. Firstly, the investigation into the rearrangement of cyclobutenediones upon treatment with lithium amides is described. This method has been studied and a wide substrate scope featuring cyclobutenediones bearing alkyl, ether and amine residues has been examined. This new rearrangement has been tested using a variety of lithium amides and has been extended to offer an efficient route to tetra-substituted furans. The rearrangement of diarylcyclobutenediones to diarylanhydrides and fused polyaromatic anhydrides has also been developed. This method involves photolysis under continuous flow using a segmented system allowing the introduction of oxygen bubbles to facilitate oxidation. Again, a wide substrate scope was examined featuring substituted aromatics and heteroaromatics leading to anhydrides in good to excellent yields.

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ORCID for David Harrowven: orcid.org/0000-0001-6730-3573

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