Lithiated azetidine and azetine chemistry
<p>This work describes developments in new azetidine and azetine chemistry; specifically, methods developed for the introduction of functionality α- to nitrogen in both ring systems, with additionally <em>in situ</em> formation of the latter system, from azetidine substrates.</p...
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| Format: | Thèse |
| Langue: | English |
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2014
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| _version_ | 1826311876730945536 |
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| author | Pearson, CI |
| author2 | Hodgson, D |
| author_facet | Hodgson, D Pearson, CI |
| author_sort | Pearson, CI |
| collection | OXFORD |
| description | <p>This work describes developments in new azetidine and azetine chemistry; specifically, methods developed for the introduction of functionality α- to nitrogen in both ring systems, with additionally <em>in situ</em> formation of the latter system, from azetidine substrates.</p> <p>Chapter 1 discusses the growing importance of azetidines, and the current methods available for making substituted azetidines by ring formation. Further discussion comprises of current sp<sup>3</sup> C–H activation approaches α- to nitrogen in heterocyclic compounds as potential methods for sp<sup>3</sup> C–H activation on azetidines to give substituted azetidines. Previous work by the Hodgson group in this area is detailed.</p> <p>Chapter 2 describes the advance made towards 2,3-disubstituted azetidines using the thiopivaloyl protecting/activating group, where the latter plays a key role. Optimisation, scope, selectivity and mechanistic insight into the α-deprotonation–electrophile trapping of a 3-hydroxy azetidine system is discussed, which successfully gives access to a range of 3-hydroxy-2-substituted azetidines. Preliminary investigations with 3-alkyl-2-substituted azetidines are also described.</p> <p>Chapter 3 describes the development of a straightforward protocol to make 2-substituted-2- azetines, a rarely studied and difficult to access 4-membered azacycle subclass, from readily accessible azetidine starting materials using α-deprotonation–<em>in situ</em> elimination followed by further α-lithiation–electrophile trapping. Extension of this methodology by transmetallation from the intermediate organolithium to the organocuprate, resulting in greater electrophile scope, is also described.</p> |
| first_indexed | 2024-03-07T08:17:44Z |
| format | Thesis |
| id | oxford-uuid:cf3c942f-80de-4092-a38d-11006ccbb9ce |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T08:17:44Z |
| publishDate | 2014 |
| record_format | dspace |
| spelling | oxford-uuid:cf3c942f-80de-4092-a38d-11006ccbb9ce2024-01-08T12:47:09ZLithiated azetidine and azetine chemistryThesishttp://purl.org/coar/resource_type/c_db06uuid:cf3c942f-80de-4092-a38d-11006ccbb9ceSynthetic organic chemistryOrganometallic ChemistryHeterocyclic chemistryOrganic chemistryOrganic synthesisEnglishOxford University Research Archive - Valet2014Pearson, CIHodgson, D<p>This work describes developments in new azetidine and azetine chemistry; specifically, methods developed for the introduction of functionality α- to nitrogen in both ring systems, with additionally <em>in situ</em> formation of the latter system, from azetidine substrates.</p> <p>Chapter 1 discusses the growing importance of azetidines, and the current methods available for making substituted azetidines by ring formation. Further discussion comprises of current sp<sup>3</sup> C–H activation approaches α- to nitrogen in heterocyclic compounds as potential methods for sp<sup>3</sup> C–H activation on azetidines to give substituted azetidines. Previous work by the Hodgson group in this area is detailed.</p> <p>Chapter 2 describes the advance made towards 2,3-disubstituted azetidines using the thiopivaloyl protecting/activating group, where the latter plays a key role. Optimisation, scope, selectivity and mechanistic insight into the α-deprotonation–electrophile trapping of a 3-hydroxy azetidine system is discussed, which successfully gives access to a range of 3-hydroxy-2-substituted azetidines. Preliminary investigations with 3-alkyl-2-substituted azetidines are also described.</p> <p>Chapter 3 describes the development of a straightforward protocol to make 2-substituted-2- azetines, a rarely studied and difficult to access 4-membered azacycle subclass, from readily accessible azetidine starting materials using α-deprotonation–<em>in situ</em> elimination followed by further α-lithiation–electrophile trapping. Extension of this methodology by transmetallation from the intermediate organolithium to the organocuprate, resulting in greater electrophile scope, is also described.</p> |
| spellingShingle | Synthetic organic chemistry Organometallic Chemistry Heterocyclic chemistry Organic chemistry Organic synthesis Pearson, CI Lithiated azetidine and azetine chemistry |
| title | Lithiated azetidine and azetine chemistry |
| title_full | Lithiated azetidine and azetine chemistry |
| title_fullStr | Lithiated azetidine and azetine chemistry |
| title_full_unstemmed | Lithiated azetidine and azetine chemistry |
| title_short | Lithiated azetidine and azetine chemistry |
| title_sort | lithiated azetidine and azetine chemistry |
| topic | Synthetic organic chemistry Organometallic Chemistry Heterocyclic chemistry Organic chemistry Organic synthesis |
| work_keys_str_mv | AT pearsonci lithiatedazetidineandazetinechemistry |