Tandem catalytic processes involving Rhodium-catalysed intermolecular hydroacylation

Thesis

This work describes the extension of rhodium-catalysed intermolecular hydroacylation to encompass some tandem catalytic processes, wherein a further catalytic process is enacted on the product of an intermolecular hydroacylation reaction in “one pot”.

Chapter 1 entails an overview of the development of hydroacylation chemistry, with a focus on the different types of catalytic systems which have been used to facilitate this transformation. A brief description of some precedented examples of tandem catalytic processes which include a hydroacylation reaction is also included.

Chapter 2 describes the intermolecular hydroacylation of chelating aldehydes and propargylic alkynes to form γ-hydroxy-α,β-enones, and their subsequent acid-catalysed cyclisation to form substituted furans in a "one-pot" procedure. Additionally, a tandem intermolecular hydroacylation/double-bond isomerisation protocol for the synthesis of 1,4-dicarbonyl compounds is detailed, and the subsequent transformation of this class of compounds to heterocycles is included.

Chapter 3 focuses on the development of tandem catalytic hydroacylation/reductive processes, wherein a hydroacylation product undergoes a reduction which is catalysed by the hydroacylation catalyst.

Chapter 4 describes an attempt to utilise the rhodium-catalysed conjugate addition of arylmetal species to enomes to create a tandem alkyne hydroacylation/conjugate addition process.

Chapter 5 encompasses the use of a small range of different solvents in rhodium-catalysed hydroacylation, in an attempt to find higher-boiling alternatives to acetone and a "green" alternative to the commonly used DCE.

Authors: Lenden, P

• Publication date: 2011
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: heterocycles; catalysis; rhodium; hydroacylation; chemistry
• Subjects: Heterocyclic chemistry; Organic synthesis; Catalysis; Organic chemistry; Organometallic Chemistry; Chemistry & allied sciences; Synthetic organic chemistry