Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes
The enantioselective intramolecular nickel-catalysed nucleophilic 1,2-allylation of ketones with (hetero)arylboronic acids or potassium vinyltrifluoroborate and progress towards the enantioselective intramolecular 1,4-allylation of enones with dialkylzinc nucleophiles are described. The first projec...
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| Format: | Thesis (University of Nottingham only) |
| Language: | English |
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2020
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| Online Access: | https://eprints.nottingham.ac.uk/59565/ |
| _version_ | 1848799646501044224 |
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| author | Di Sanza, Riccardo |
| author_facet | Di Sanza, Riccardo |
| author_sort | Di Sanza, Riccardo |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | The enantioselective intramolecular nickel-catalysed nucleophilic 1,2-allylation of ketones with (hetero)arylboronic acids or potassium vinyltrifluoroborate and progress towards the enantioselective intramolecular 1,4-allylation of enones with dialkylzinc nucleophiles are described. The first project is initiated by carbonickelation of allenes which gives the nucleophilic allylnickel species that cyclise by 1,2-allylation onto a tethered ketone to produce a range of chiral tertiaryalcohol containing aza- and carbocycles in excellent diastereo- and enantioselectivities. The second project is initiated by the oxidative cyclisation of Pd(0) with an allene tethered to an enone. The resulting palladacycle formed undergoes transmetalation with a dialkylzinc nucleophile, and subsequent reductive elimination affords 6,5-fused bicycles in high diastereoselectivity. |
| first_indexed | 2025-11-14T20:38:58Z |
| format | Thesis (University of Nottingham only) |
| id | nottingham-59565 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T20:38:58Z |
| publishDate | 2020 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-595652025-02-28T14:44:05Z https://eprints.nottingham.ac.uk/59565/ Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes Di Sanza, Riccardo The enantioselective intramolecular nickel-catalysed nucleophilic 1,2-allylation of ketones with (hetero)arylboronic acids or potassium vinyltrifluoroborate and progress towards the enantioselective intramolecular 1,4-allylation of enones with dialkylzinc nucleophiles are described. The first project is initiated by carbonickelation of allenes which gives the nucleophilic allylnickel species that cyclise by 1,2-allylation onto a tethered ketone to produce a range of chiral tertiaryalcohol containing aza- and carbocycles in excellent diastereo- and enantioselectivities. The second project is initiated by the oxidative cyclisation of Pd(0) with an allene tethered to an enone. The resulting palladacycle formed undergoes transmetalation with a dialkylzinc nucleophile, and subsequent reductive elimination affords 6,5-fused bicycles in high diastereoselectivity. 2020-03-15 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en arr https://eprints.nottingham.ac.uk/59565/1/Riccardo%20Di%20Sanza%20Thesis%20Corrected.pdf Di Sanza, Riccardo (2020) Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes. PhD thesis, University of Nottingham. Chiral pyrrolidin-2-ones; Nucleophilic allylation; Tertiary alcohol; Ketones; High enantioselectivity; Nickel catalysis |
| spellingShingle | Chiral pyrrolidin-2-ones; Nucleophilic allylation; Tertiary alcohol; Ketones; High enantioselectivity; Nickel catalysis Di Sanza, Riccardo Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes |
| title | Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes |
| title_full | Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes |
| title_fullStr | Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes |
| title_full_unstemmed | Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes |
| title_short | Studies towards enantioselective metal-catalysed nucleophilic allylations using allenes |
| title_sort | studies towards enantioselective metal-catalysed nucleophilic allylations using allenes |
| topic | Chiral pyrrolidin-2-ones; Nucleophilic allylation; Tertiary alcohol; Ketones; High enantioselectivity; Nickel catalysis |
| url | https://eprints.nottingham.ac.uk/59565/ |