New applications of rhodium-catalysed hydroacylation

Thesis

This thesis describes the development of two new rhodium-catalysed hydroacylation methods. The first involves a one-pot hydroacylation/thio-conjugate addition cascade towards the synthesis of fully saturated sulfur heterocycles. The second exploits novel β-sulfonyl aldehydes to access β-keto-sulfones and sulfonamides.

Chapter 1 delineates a literature review of the evolution of rhodium-catalysed hydroacylation, with focus on catalyst design and chelating groups that hinder decarbonylation. The use of hydroacylation in heterocycle synthesis is also briefly reviewed.

Chapter 2 documents the use of alkynes with pendant sulfur nucleophiles in a highly regioselective rhodium-catalysed hydroacylation reaction, delivering linear α,β-unsaturated enone intermediates. These adducts are further harnessed in intramolecular cyclisation reactions to access diversely substituted, saturated S-heterocycles, in a one-pot fashion.

Chapter 3 outlines initial attempts to develop a rhodium-catalysed hydroacylation methodology for the synthesis of β-keto-sulfones and sulfonamides. The work explores the construction of new β-sulfonyl aldehydes and their use in intermolecular hydroacylation.

Chapter 4 presents the conclusions from the research conducted and future work.

Chapter 5 details the experimental data and procedures.

Authors: Iwumene, NUN

• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: cyclisation; rhodium catalysis; hydroacylation
• Subjects: Organic compounds--Synthesis