Nickel-Catalysed Arylative Cyclisations of Alkynones & Molecular Editing of Cyclic Ketones
PART I: NICKEL-CATALYSED ANTI-ARYLMETALLATIVE CYCLISATIONS ONTO KETONES A highly enantioselective and regioselective nickel-catalysed domino reaction of the addition of boronic acids across an alkyne, followed by subsequent cyclisation onto a ketone is reported. The reversible E/Z isomerization of...
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| Format: | Thesis (University of Nottingham only) |
| Language: | English |
| Published: |
2023
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| Online Access: | https://eprints.nottingham.ac.uk/72269/ |
| _version_ | 1848801196826951680 |
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| author | Green, Harley |
| author_facet | Green, Harley |
| author_sort | Green, Harley |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | PART I: NICKEL-CATALYSED ANTI-ARYLMETALLATIVE CYCLISATIONS ONTO KETONES
A highly enantioselective and regioselective nickel-catalysed domino reaction of the addition of boronic acids across an alkyne, followed by subsequent cyclisation onto a ketone is reported. The reversible E/Z isomerization of the alkenylnickel intermediate is key to enable the overall anti-arylmetallative cyclisation. The process affords enantioenriched tertiary-alcohol-containing products of which the ring system is featured in several diarylindolizidine alkaloids.
PART II: MOLECULAR EDITING OF CYCLIC KETONES: C-TO-N ATOM EXCHANGE
A process for the molecular editing of α-substituted cyclic ketones by performing a formal C-to-N atom exchange is reported. The key first step involves ring-opening the ketone, with the ketoacid product being leveraged through a Curtius rearrangement to introduce the nitrogen atom. Finally, a ring closing step forms the C-to-N atom exchanged product. This process involves simple air-tolerant chemistry, and the products themselves can be purified without the need for column chromatography with a preliminary scope of five compounds being reported. |
| first_indexed | 2025-11-14T20:56:11Z |
| format | Thesis (University of Nottingham only) |
| id | nottingham-72269 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T21:03:37Z |
| publishDate | 2023 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-722692025-07-31T04:30:10Z https://eprints.nottingham.ac.uk/72269/ Nickel-Catalysed Arylative Cyclisations of Alkynones & Molecular Editing of Cyclic Ketones Green, Harley PART I: NICKEL-CATALYSED ANTI-ARYLMETALLATIVE CYCLISATIONS ONTO KETONES A highly enantioselective and regioselective nickel-catalysed domino reaction of the addition of boronic acids across an alkyne, followed by subsequent cyclisation onto a ketone is reported. The reversible E/Z isomerization of the alkenylnickel intermediate is key to enable the overall anti-arylmetallative cyclisation. The process affords enantioenriched tertiary-alcohol-containing products of which the ring system is featured in several diarylindolizidine alkaloids. PART II: MOLECULAR EDITING OF CYCLIC KETONES: C-TO-N ATOM EXCHANGE A process for the molecular editing of α-substituted cyclic ketones by performing a formal C-to-N atom exchange is reported. The key first step involves ring-opening the ketone, with the ketoacid product being leveraged through a Curtius rearrangement to introduce the nitrogen atom. Finally, a ring closing step forms the C-to-N atom exchanged product. This process involves simple air-tolerant chemistry, and the products themselves can be purified without the need for column chromatography with a preliminary scope of five compounds being reported. 2023-07-31 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en cc_by https://eprints.nottingham.ac.uk/72269/1/Harley%20Green%20Thesis%20%28Corrected%29.pdf Green, Harley (2023) Nickel-Catalysed Arylative Cyclisations of Alkynones & Molecular Editing of Cyclic Ketones. PhD thesis, University of Nottingham. alkynes ketones alkenes heterocyclic chemistry |
| spellingShingle | alkynes ketones alkenes heterocyclic chemistry Green, Harley Nickel-Catalysed Arylative Cyclisations of Alkynones & Molecular Editing of Cyclic Ketones |
| title | Nickel-Catalysed Arylative Cyclisations of Alkynones & Molecular Editing of Cyclic Ketones |
| title_full | Nickel-Catalysed Arylative Cyclisations of Alkynones & Molecular Editing of Cyclic Ketones |
| title_fullStr | Nickel-Catalysed Arylative Cyclisations of Alkynones & Molecular Editing of Cyclic Ketones |
| title_full_unstemmed | Nickel-Catalysed Arylative Cyclisations of Alkynones & Molecular Editing of Cyclic Ketones |
| title_short | Nickel-Catalysed Arylative Cyclisations of Alkynones & Molecular Editing of Cyclic Ketones |
| title_sort | nickel-catalysed arylative cyclisations of alkynones & molecular editing of cyclic ketones |
| topic | alkynes ketones alkenes heterocyclic chemistry |
| url | https://eprints.nottingham.ac.uk/72269/ |