Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations
Herein is described the catalytic in situ generation of nucleophilic allylmetal species through the activation of allylic C-H bonds. Reactivity is achieved through initial carbometalation of an enyne, followed by the key 1,4-alkenyl-to-allyl metal migration which generates the allylmetal intermediat...
| Main Author: | |
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| Format: | Thesis (University of Nottingham only) |
| Language: | English |
| Published: |
2018
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| Online Access: | https://eprints.nottingham.ac.uk/52053/ |
| _version_ | 1848798637013860352 |
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| author | Callingham, Michael |
| author_facet | Callingham, Michael |
| author_sort | Callingham, Michael |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | Herein is described the catalytic in situ generation of nucleophilic allylmetal species through the activation of allylic C-H bonds. Reactivity is achieved through initial carbometalation of an enyne, followed by the key 1,4-alkenyl-to-allyl metal migration which generates the allylmetal intermediate.
This new mode of reactivity was firstly employed in the rhodium-catalysed diastereoselective reaction of arylboron reagents with enynones, to give products containing three contiguous stereocentres. Initial discovery and optimisation of this reaction was performed by Benjamin Partridge. Through use of a chiral sulfur olefin ligand, products could be obtained in high enantioselectivites.
Secondly, a three-component coupling between 1,3-enynes, arylboronic acids and imines is described. The use of a chiral rhodium catalyst allowed the synthesis of a range of homoallylic amines with excellent control of stereoselectivity (>95:5 dr, up to 99% ee). |
| first_indexed | 2025-11-14T20:22:56Z |
| format | Thesis (University of Nottingham only) |
| id | nottingham-52053 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T20:22:56Z |
| publishDate | 2018 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-520532025-02-28T14:08:16Z https://eprints.nottingham.ac.uk/52053/ Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations Callingham, Michael Herein is described the catalytic in situ generation of nucleophilic allylmetal species through the activation of allylic C-H bonds. Reactivity is achieved through initial carbometalation of an enyne, followed by the key 1,4-alkenyl-to-allyl metal migration which generates the allylmetal intermediate. This new mode of reactivity was firstly employed in the rhodium-catalysed diastereoselective reaction of arylboron reagents with enynones, to give products containing three contiguous stereocentres. Initial discovery and optimisation of this reaction was performed by Benjamin Partridge. Through use of a chiral sulfur olefin ligand, products could be obtained in high enantioselectivites. Secondly, a three-component coupling between 1,3-enynes, arylboronic acids and imines is described. The use of a chiral rhodium catalyst allowed the synthesis of a range of homoallylic amines with excellent control of stereoselectivity (>95:5 dr, up to 99% ee). 2018-07-19 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en arr https://eprints.nottingham.ac.uk/52053/1/Michael%20Callingham%20-%20Corrected%20Thesis.pdf Callingham, Michael (2018) Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations. PhD thesis, University of Nottingham. |
| spellingShingle | Callingham, Michael Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations |
| title | Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations |
| title_full | Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations |
| title_fullStr | Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations |
| title_full_unstemmed | Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations |
| title_short | Reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations |
| title_sort | reactions of nucleophilic allymetal species generated in situ through 1,4-alkenyl-to-allyl metal migrations |
| url | https://eprints.nottingham.ac.uk/52053/ |