Ketone synthesis via rhodium-catalyzed traceless chelation-controlled hydroacylation reactions

Thesis

This thesis documents the development of rhodium-catalyzed traceless chelation-controlled hydroacylation reactions for the synthesis of a variety of ketone products.

Chapter 1 provides an overview of rhodium-catalyzed hydroacylation chemistry, focusing on the origin of chelation-controlled strategies and the benefits thereof.

Chapter 2 describes a sequential reaction involving alkene hydroacylation, sulfide elimination and boronic acid conjugate addition, which affords products with the initial sulfide coordinating group replaced by a stereochemically defined aryl group.

Chapter 3 demonstrates a sequential process involving alkyne hydroacylation, boronic acid conjugate addition and sulfide elimination, which provides enantioenriched β’-arylα,β-unsaturated ketones in a highly efficient and selective manner.

Chapter 4 illustrates a versatile chelating group, triazene, for hydroacylation reactions. Subsequent functionalization of aromatic C-H bonds, promoted by the same chelating unit, offers highly substituted phenyl ketone products.

Chapter 5 documents experimental procedures and data.

Authors: Gao, M

• DOI: 10.5287/ora-erjj4v5v8
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: asymmetric catalysis; rhodium catalyst; cascade reaction
• Subjects: Rhodium Catalysis; Chemistry, Organic; Hydroacylation