Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles

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Edmonds, Alex (2024) Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles. PhD thesis, University of Nottingham.

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Abstract

Electrosynthetic methods are of growing contemporary interest, due to the unique reactivity that they can facilitate, and their potential for improved sustainability compared to conventional methods. This thesis discusses the development of two different electrosynthetic reactions.

We disclose the electrochemical deoxygenation of benzylic alcohols using an electrochemically-generated phosphine radical cation. The scope and functional group tolerance of the chemistry is explored, and yields of up to 98% were achieved. The deoxygenation is specific to benzylic alcohols, and chemical, electrochemical and computational investigations provide insight into the operative mechanism of the transformation. Additionally, attempts to develop an electrochemical dehydroxylative functionalisation reaction are briefly discussed.

The development of an electrochemical route to spirocycles from β-hydroxyacids is outlined, and the scope and functional group tolerance of the chemistry is explored. The reaction was carried out in flow, achieving a yield of 43% under unoptimised conditions.

Item Type: Thesis (University of Nottingham only) (PhD)
Supervisors: Cuthbertson, James
Walsh, Darren
Keywords: Electrochemistry, Electrosynthesis, Deoxygenation, Phosphoranyl Radical, Semipinacol Rearrangement, Spirocycles
Subjects: Q Science > QD Chemistry > QD 71 Analytical chemistry
Q Science > QD Chemistry > QD241 Organic chemistry
Faculties/Schools: UK Campuses > Faculty of Science > School of Chemistry
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URL Type
http://doi.org/10.17639/nott.7416
Dataset
Item ID: 78215
Depositing User: Edmonds, Alex
Date Deposited: 24 Jul 2024 04:43
Last Modified: 24 Jul 2024 04:43
URI: https://eprints.nottingham.ac.uk/id/eprint/78215

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