Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization
Herein is described the first enantioselective intramolecular allylation of alkenylnickel nucleophiles. These reactions are initiated by the addition of an arylboronic acid across an alkyne, followed by cyclization of the resulting alkenylnickel species onto an allylic phosphate. The reversible E/Z...
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| Format: | Thesis (University of Nottingham only) |
| Language: | English |
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2019
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| Online Access: | https://eprints.nottingham.ac.uk/55829/ |
| _version_ | 1848799223843127296 |
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| author | Yap, Connor |
| author_facet | Yap, Connor |
| author_sort | Yap, Connor |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | Herein is described the first enantioselective intramolecular allylation of alkenylnickel nucleophiles. These reactions are initiated by the addition of an arylboronic acid across an alkyne, followed by cyclization of the resulting alkenylnickel species onto an allylic phosphate. The reversible E/Z isomerization of the alkenylnickel species is essential for the success of the reactions.
This process delivers chiral 1,4-diene-containing hetero- and carbocycles, previously inaccessible via established rhodium catalysis, with excellent levels of regio- and stereocontrol. This reaction further demonstrates the power of reversible alkenylnickel E/Z isomerization in providing products that would otherwise be inaccessible using syn-selective alkyne carbometallation processes.
Attempts to extend this reactivity to other classes of electrophilic traps are also described. |
| first_indexed | 2025-11-14T20:32:15Z |
| format | Thesis (University of Nottingham only) |
| id | nottingham-55829 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T20:32:15Z |
| publishDate | 2019 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-558292025-02-28T14:21:07Z https://eprints.nottingham.ac.uk/55829/ Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization Yap, Connor Herein is described the first enantioselective intramolecular allylation of alkenylnickel nucleophiles. These reactions are initiated by the addition of an arylboronic acid across an alkyne, followed by cyclization of the resulting alkenylnickel species onto an allylic phosphate. The reversible E/Z isomerization of the alkenylnickel species is essential for the success of the reactions. This process delivers chiral 1,4-diene-containing hetero- and carbocycles, previously inaccessible via established rhodium catalysis, with excellent levels of regio- and stereocontrol. This reaction further demonstrates the power of reversible alkenylnickel E/Z isomerization in providing products that would otherwise be inaccessible using syn-selective alkyne carbometallation processes. Attempts to extend this reactivity to other classes of electrophilic traps are also described. 2019-07-17 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en arr https://eprints.nottingham.ac.uk/55829/1/CY%20Corrected%20Thesis.pdf Yap, Connor (2019) Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization. PhD thesis, University of Nottingham. Enantioselective intramolecular allylation; Alkenylnickel nucleophiles |
| spellingShingle | Enantioselective intramolecular allylation; Alkenylnickel nucleophiles Yap, Connor Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization |
| title | Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization |
| title_full | Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization |
| title_fullStr | Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization |
| title_full_unstemmed | Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization |
| title_short | Nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel E/Z isomerization |
| title_sort | nickel-catalyzed arylative cyclizations enabled by reversible alkenylnickel e/z isomerization |
| topic | Enantioselective intramolecular allylation; Alkenylnickel nucleophiles |
| url | https://eprints.nottingham.ac.uk/55829/ |