Hydrogen bonding phase-transfer catalysis with sodium azide and potassium cyanide

Thesis

Hydrogen Bonding-Phase Transfer Catalysis (HB-PTC) enables use of alkali metal fluoride salts as reactive reagents in enantioselective catalysis and this platform has been successfully applied towards enantioselective fluorination. This thesis details a study into the structure and reactivity of hydrogen bonded azide and cyanide anions and the development of enantioselective reactions using sodium azide and potassium cyanide under HB-PTC for the synthesis of enantioenriched organoazide and organonitriles.

The first chapter introduces phase-transfer catalysis and discusses the advantages of HB-PTC. The second chapter presents a detailed study into the structure and coordination of hydrogen bonded azide complexes in both solid state and solution, and discusses the development and mechanistic study of an enantioselective azidation reaction with sodium azide under HB-PTC. The third chapter describes the structure and coordination of hydrogen bonded cyanide complexes in both solid state and solution and details the development of an enantioselective cyanation reaction with potassium cyanide under HB-PTC. The final chapter contains supporting information including experimental procedures and characterisation data. An appendix with additional crystal structures is also included.

Authors: Wang, J

• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: sodium azide; potassium cyanide; HB-PTC; hydrogen bonding; Phase Transfer Catalysis
• Subjects: Chemistry; Chemistry, Organic