Photochemical transformations of α-diazocarbonyl compounds in flow

This thesis describes a detailed investigation of the synthetic and mechanistic aspects of the reactivity of a series of α-diazocarbonyl compounds including aryldiazoacetates, α-diazo-β-ketoesters and an α-diazo-β-ketosulfone, under continuous flow photolysis. These photochemical transformations yielded 2,3-dihydrobenzofurans, γ- and β-lactones, oxazoles and Wolff rearrangement products indicating the synthetic versatility of these metal-free processes. Continuous flow technology was also applied to telescope sulfonyl azide generation, diazo transfer and subsequent photochemical reactions, enabling three steps to be carried out without the need to isolate or handle any hazardous materials. The use of Process Analytical Technologies (FlowNMR and FlowIR™) throughout this work provided key insights into reaction progress and offered improved process safety through reaction monitoring.

Grantor dc:publisher

University College Cork

Year dc:date.issued

2024

Author dc:creator

• O'Callaghan, Katie S.

Advisors dc:contributor.advisor

• Maguire, Anita
• Collins, Stuart

• α-Diazocarbonyl compounds
• Photochemistry
• Flow chemistry

Statement dc:rights

• © 2024, Katie O'Callaghan.

Licence dc:rights.uri

• https://creativecommons.org/licenses/by/4.0/

Language dc:language.iso

en

Handle dc:identifier.uri

https://hdl.handle.net/10468/17000

OAI identifier oai:identifier

oai:cora.ucc.ie:10468/17000