Enantioselective Nickel-Catalysed Arylative and Alkenylative Cyclisations onto Electron-Deficient Alkenes via E/Z Isomerisation
Herein is presented a highly enantioselective nickel-catalysed anti-carbometallative-cyclisation reaction of substrates containing an alkyne tethered to an electron-deficient alkene. Enantioenriched cyclopentene products, that are otherwise difficult to synthesise, are obtained in up to 99% yield an...
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| Format: | Thesis (University of Nottingham only) |
| Language: | English |
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2023
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| Online Access: | https://eprints.nottingham.ac.uk/73697/ |
| _version_ | 1848800804522164224 |
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| author | Gillbard, Simone Marie |
| author_facet | Gillbard, Simone Marie |
| author_sort | Gillbard, Simone Marie |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | Herein is presented a highly enantioselective nickel-catalysed anti-carbometallative-cyclisation reaction of substrates containing an alkyne tethered to an electron-deficient alkene. Enantioenriched cyclopentene products, that are otherwise difficult to synthesise, are obtained in up to 99% yield and >99% ee. The overall anti-carbometalation of the alkyne is enabled by the critical reversible E/Z isomerisation of alkenylnickel intermediates.
Investigation of the substrate scope revealed that alkyne substituents such as (hetero)aryl and alkenyl groups were compatible with the reaction and substrates containing electron-deficient alkenes such as α,β-unsaturated alkyl or (hetero)aryl ketones, nitroalkenes, α,β-unsaturated esters and alkenyl nitriles successfully participated in the reaction. Also, (hetero)arylboronic acid as well as alkenylboronic acids were tolerated in the reaction.
Efforts were made towards the synthesis of enantioenriched 6-membered carbo- and heterocyclic products by extending the tether between the alkyne and the electron-deficient alkene in the substrate. |
| first_indexed | 2025-11-14T20:57:23Z |
| format | Thesis (University of Nottingham only) |
| id | nottingham-73697 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T20:57:23Z |
| publishDate | 2023 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-736972023-07-26T04:40:36Z https://eprints.nottingham.ac.uk/73697/ Enantioselective Nickel-Catalysed Arylative and Alkenylative Cyclisations onto Electron-Deficient Alkenes via E/Z Isomerisation Gillbard, Simone Marie Herein is presented a highly enantioselective nickel-catalysed anti-carbometallative-cyclisation reaction of substrates containing an alkyne tethered to an electron-deficient alkene. Enantioenriched cyclopentene products, that are otherwise difficult to synthesise, are obtained in up to 99% yield and >99% ee. The overall anti-carbometalation of the alkyne is enabled by the critical reversible E/Z isomerisation of alkenylnickel intermediates. Investigation of the substrate scope revealed that alkyne substituents such as (hetero)aryl and alkenyl groups were compatible with the reaction and substrates containing electron-deficient alkenes such as α,β-unsaturated alkyl or (hetero)aryl ketones, nitroalkenes, α,β-unsaturated esters and alkenyl nitriles successfully participated in the reaction. Also, (hetero)arylboronic acid as well as alkenylboronic acids were tolerated in the reaction. Efforts were made towards the synthesis of enantioenriched 6-membered carbo- and heterocyclic products by extending the tether between the alkyne and the electron-deficient alkene in the substrate. 2023-07-26 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en cc_by https://eprints.nottingham.ac.uk/73697/1/PhD%20Thesis%20-%20Simone%20Gillbard%20Corrected.pdf Gillbard, Simone Marie (2023) Enantioselective Nickel-Catalysed Arylative and Alkenylative Cyclisations onto Electron-Deficient Alkenes via E/Z Isomerisation. PhD thesis, University of Nottingham. heterocycles electrophiles catalysis domino reactions |
| spellingShingle | heterocycles electrophiles catalysis domino reactions Gillbard, Simone Marie Enantioselective Nickel-Catalysed Arylative and Alkenylative Cyclisations onto Electron-Deficient Alkenes via E/Z Isomerisation |
| title | Enantioselective Nickel-Catalysed Arylative and Alkenylative Cyclisations onto Electron-Deficient Alkenes via E/Z Isomerisation |
| title_full | Enantioselective Nickel-Catalysed Arylative and Alkenylative Cyclisations onto Electron-Deficient Alkenes via E/Z Isomerisation |
| title_fullStr | Enantioselective Nickel-Catalysed Arylative and Alkenylative Cyclisations onto Electron-Deficient Alkenes via E/Z Isomerisation |
| title_full_unstemmed | Enantioselective Nickel-Catalysed Arylative and Alkenylative Cyclisations onto Electron-Deficient Alkenes via E/Z Isomerisation |
| title_short | Enantioselective Nickel-Catalysed Arylative and Alkenylative Cyclisations onto Electron-Deficient Alkenes via E/Z Isomerisation |
| title_sort | enantioselective nickel-catalysed arylative and alkenylative cyclisations onto electron-deficient alkenes via e/z isomerisation |
| topic | heterocycles electrophiles catalysis domino reactions |
| url | https://eprints.nottingham.ac.uk/73697/ |