Photocatalytic reductive synthesis of α-functionalised amines and ethers

Thesis

Chapter 1 introduces fundamental notions of photocatalysis as well as its evolution into mod- ern photoredox catalysis with seminal contributions of the past decade.

Chapter 2 describes the development of a photocatalytic three-component one-pot umpolung methodology for the diastereoselective synthesis of 1,3-diamines based on the in situ formation of nucleophilic α-amino radicals species. The method provides access to a broad range of 1,3- diamine products with a wide variety of functionalities and demonstrates its application as an entry point to bioactive molecules.

Chapter 3 details the design and application of a reductive synthetic methodolgy for the construction of challenging α-tertiary dialkyl ether compounds from readily accessible starting materials. The coupling approach pivots on a novel photocatalytic single-electron reduction of oxocarbenium ion intermediates.

Chapter 4 illustrates our efforts towards the development of a photocatalyst-free approach for the synthesis of biologically relevant α-trifluoromethyl-α-amino acid derivatives. Visible light-mediated homolytic cleavage of substituted radical precursors (RPs) is used to generate open-shell alkyl species which are believed to engage in radical addition reactions.

Authors: Rossolini, T

• DOI: 10.5287/ora-qm0dv0okz
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: umpolung; photoredox; catalysis
• Subjects: Photoredox Catalysis