Synthesis and reactivity of α-diazosulfoxides and α-diazosulfones

The focus of this body of work has been the synthesis of stable mono and bicyclic α-diazosulfoxides and their subsequent reactivity. A range of α-diazosulfoxides have been synthesised by the Maguire-Collins research group since the mid-1990s using a Regitz diazo transfer method. In this work in situ NMR monitoring has been used to gain a deeper understanding of the relative reactivity of diastereomeric sulfoxides in this reaction. α-Diazosulfoxides were synthesised using flow and batch reaction conditions. Continuous flow processing enabled the α-diazosulfoxide synthesis using an in situ generated sulfonyl azide for the first time, resulting in a greater safety profile for the process. Investigations into the synthesis of related mono and bicyclic α-diazosulfones were also undertaken, in both batch and flow. The α-diazosulfoxides are known to react via a hetero-Wolff rearrangement to form α-oxo sulfines. The 1,3-dipolar cycloadditions of these α-oxo sulfines were investigated further under Rh catalysis and a study into the photoreactivity of the α-diazosulfoxides on flow was also performed.

Grantor dc:publisher

University College Cork

Year dc:date.issued

2024

Author dc:creator

• Ní Thuama, Eilís

Advisors dc:contributor.advisor

• Maguire, Anita
• Collins, Stuart

• Diazosulfoxides
• Diazosulfones
• Flow chemistry
• Continuous processing

Statement dc:rights

• © 2024, Eilís Ní Thuama.

Licence dc:rights.uri

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

Language dc:language.iso

en

Handle dc:identifier.uri

https://hdl.handle.net/10468/16999

OAI identifier oai:identifier

oai:cora.ucc.ie:10468/16999