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Title: Coupling reactions using flow-generated diazo compounds
Author: Poh, Jian Siang
ISNI:       0000 0004 7224 6309
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2017
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In recent years, the exploitation of flow technologies as an enabling tool to access unique chemical reactivity has flourished. This dissertation describes the utilisation of these flow methods to access new sets of highly versatile, unstable diazo compounds and their application in coupling reactions. In the first chapter, an introduction into the structure and reactivity of diazo compounds is provided, as well as a discussion of currently available methods for their generation. The second chapter describes the coupling of flow-generated, semi-stabilised diazo compounds with terminal alkynes for the synthesis of racemic di- and trisubstituted allenes, using copper(I) catalysis. The third chapter follows with an account of creating chiral disubstituted allenes by asymmetric coupling of flow-generated, semi-stabilised aryl aldehyde-derived diazo compounds with terminal alkynes, using a copper(I) catalyst and a newly developed pyridine(bisimidazoline) ligand. The fourth chapter describes the generation of new, highly reactive non-stabilised diazo compounds and their reaction with arylboronic acids to allow metal-free ‘protodeboronative’ and ‘oxidative’ C(sp2)-C(sp3) cross-couplings. Finally, the fifth chapter describes the experimental procedures relevant for the results described in Chapters 2-4.
Supervisor: Ley, Steven Victor Sponsor: Cambridge Home and EU Scholarship Scheme (CHESS) ; UCB Biopharma SPRL
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
Keywords: allenes ; copper ; diazo compounds ; flow chemistry ; coupling reactions ; asymmetric catalysis ; photochemistry