New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration
The Rh(III)-catalysed oxidative C–H allylation and homoallylation of N-acetylbenzamides with 1,3-dienes is described. The presence of allylic hydrogens cis to the less substituted alkene of the 1,3-diene is important for the success of these reactions, though not essential. With the assistance of re...
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| Format: | Thesis (University of Nottingham only) |
| Language: | English |
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2018
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| Online Access: | https://eprints.nottingham.ac.uk/48787/ |
| _version_ | 1848797846792306688 |
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| author | Korkis, Stamatis E. |
| author_facet | Korkis, Stamatis E. |
| author_sort | Korkis, Stamatis E. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | The Rh(III)-catalysed oxidative C–H allylation and homoallylation of N-acetylbenzamides with 1,3-dienes is described. The presence of allylic hydrogens cis to the less substituted alkene of the 1,3-diene is important for the success of these reactions, though not essential. With the assistance of reactions using deuterated 1,3-dienes, a proposed mechanism is provided. The key step is postulated to be the first reported examples of allyl-to-allyl 1,4-Rh(III) migration. Importantly, migration to primary or secondary allylic position results in allylation products, whereas migration to a tertiary position leads to homoallylation. Using 1,4-dienes as the coupling partner, N-tosylbenzamides are homoallylated. Preliminary results indicate a mixture of isomer products, with major isomer resulting from an allyl-to-allyl 1,4-Rh(III) migration. |
| first_indexed | 2025-11-14T20:10:22Z |
| format | Thesis (University of Nottingham only) |
| id | nottingham-48787 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T20:10:22Z |
| publishDate | 2018 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-487872025-02-28T13:57:08Z https://eprints.nottingham.ac.uk/48787/ New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration Korkis, Stamatis E. The Rh(III)-catalysed oxidative C–H allylation and homoallylation of N-acetylbenzamides with 1,3-dienes is described. The presence of allylic hydrogens cis to the less substituted alkene of the 1,3-diene is important for the success of these reactions, though not essential. With the assistance of reactions using deuterated 1,3-dienes, a proposed mechanism is provided. The key step is postulated to be the first reported examples of allyl-to-allyl 1,4-Rh(III) migration. Importantly, migration to primary or secondary allylic position results in allylation products, whereas migration to a tertiary position leads to homoallylation. Using 1,4-dienes as the coupling partner, N-tosylbenzamides are homoallylated. Preliminary results indicate a mixture of isomer products, with major isomer resulting from an allyl-to-allyl 1,4-Rh(III) migration. 2018-03-15 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en arr https://eprints.nottingham.ac.uk/48787/1/Chemistry%20PhD%20Thesis%20corrected%20S.Korkis.pdf Korkis, Stamatis E. (2018) New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration. PhD thesis, University of Nottingham. Rh(III)-catalysis directed and remote C-H functionalisation 1 4-migration 1 4-allylic transposition chain-walking allylic isomerisation β-hydride elimination |
| spellingShingle | Rh(III)-catalysis directed and remote C-H functionalisation 1 4-migration 1 4-allylic transposition chain-walking allylic isomerisation β-hydride elimination Korkis, Stamatis E. New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration |
| title | New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration |
| title_full | New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration |
| title_fullStr | New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration |
| title_full_unstemmed | New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration |
| title_short | New reactive sites enabled via an allyl-to-allyl 1,4-Rh(III) migration |
| title_sort | new reactive sites enabled via an allyl-to-allyl 1,4-rh(iii) migration |
| topic | Rh(III)-catalysis directed and remote C-H functionalisation 1 4-migration 1 4-allylic transposition chain-walking allylic isomerisation β-hydride elimination |
| url | https://eprints.nottingham.ac.uk/48787/ |