Applications of DABSO in metal catalysis

Thesis

Chapter 1 discusses the importance of the sulfonyl moiety in biological compounds and the developments in the use of sulfur dioxide and sulfur dioxide donors in metal catalysis and organic synthesis.

Chapter 2 focuses on the serendipitous discovery, optimisation and exploration of a route towards the synthesis of sulfones via an N-aminosulfonamide intermediate exploiting both palladium-catalysed aminosulfonylation and the predisposition of N aminosulfonamides to decompose to the sulfinate salt (Scheme 1).

Scheme 1

Chapter 3 investigates the synthesis of benzosultams with an aryl-N-SO2 linkage. A range of benzosultams and its derivatives were prepared after optimisation of a synthetic sequence involving palladium-catalysed aminosulfonylation and a subsequent Buchwald– Hartwig coupling (Scheme 2).

Scheme 2

Chapter 4 describes efforts towards the synthesis of a benzosultam with an aryl-SO2-N linkage through various precursors and metal-catalysed routes using DABSO as the sulfur dioxide source (Figure 1).

Figure 1

Chapter 5 provides a summary of this thesis and outlines possibilities for future work.

Chapter 6 provides experimental details and data for compounds discussed in this thesis.

Appendix A details a brief investigation into the synthesis of N aminosulfonamides from heteroaryl iodides as an extension of the Willis group palladium-catalysed aminosulfonylation reaction (Scheme 3).

Scheme 3

Appendix B presents 1H and 13C NMR spectra as well as X-ray crystallographic data of key compounds.

Authors: Richards-Taylor, C

• Publication date: 2014
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: chemistry
• Subjects: Organic chemistry