Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles

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 t...

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Main Author: Edmonds, Alex
Format: Thesis (University of Nottingham only)
Language:English
Published: 2024
Subjects:
Online Access:https://eprints.nottingham.ac.uk/78215/
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author Edmonds, Alex
author_facet Edmonds, Alex
author_sort Edmonds, Alex
building Nottingham Research Data Repository
collection Online Access
description 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.
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format Thesis (University of Nottingham only)
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institution University of Nottingham Malaysia Campus
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language English
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publishDate 2024
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spelling nottingham-782152025-02-28T15:20:58Z https://eprints.nottingham.ac.uk/78215/ Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles Edmonds, Alex 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. 2024-07-24 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en cc_by https://eprints.nottingham.ac.uk/78215/1/Edmonds%2C%20Alex%2C%2014255927%2C%20Corrected%20Thesis.pdf Edmonds, Alex (2024) Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles. PhD thesis, University of Nottingham. Electrochemistry Electrosynthesis Deoxygenation Phosphoranyl Radical Semipinacol Rearrangement Spirocycles
spellingShingle Electrochemistry
Electrosynthesis
Deoxygenation
Phosphoranyl Radical
Semipinacol Rearrangement
Spirocycles
Edmonds, Alex
Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles
title Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles
title_full Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles
title_fullStr Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles
title_full_unstemmed Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles
title_short Electrochemical Deoxygenation of Benzylic Alcohols and Electrosynthesis of Spirocycles
title_sort electrochemical deoxygenation of benzylic alcohols and electrosynthesis of spirocycles
topic Electrochemistry
Electrosynthesis
Deoxygenation
Phosphoranyl Radical
Semipinacol Rearrangement
Spirocycles
url https://eprints.nottingham.ac.uk/78215/