Palladium-catalysed cyclisations of bromoenynamides in the synthesis and applications of amidodienes
<p>The aim of this work was to investigate palladium-catalysed cyclisations of bromoenynamides in the synthesis of amidodienes, which on further reaction or oxidation can lead to a diverse range of heteroaromatic systems.</p> <p>Building upon work within the Anderson group on the p...
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| Format: | Thesis |
| Language: | English |
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2013
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| _version_ | 1797097036106956800 |
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| author | Greenaway, R |
| author2 | Anderson, E |
| author_facet | Anderson, E Greenaway, R |
| author_sort | Greenaway, R |
| collection | OXFORD |
| description | <p>The aim of this work was to investigate palladium-catalysed cyclisations of bromoenynamides in the synthesis of amidodienes, which on further reaction or oxidation can lead to a diverse range of heteroaromatic systems.</p> <p>Building upon work within the Anderson group on the palladium-catalysed cyclisations of bromoenynes, we have been able to successfully apply a palladium-catalysed carbopalladation/Stille coupling/electrocyclisation cascade to bromoenynamides and then further develop this to incorporate a Suzuki coupling, leading to bicyclic amidodienes which can undergo selective oxidation to a range of heteroaromatics including indolines, indoles, tetrahydroquinolines and benzazepines.</p> <p>During the investigations into the cascade cyclisation, a reductive cyclisation was discovered which enabled access to a range of monocyclic amidodienes. These could subsequently be subjected to a series of Diels-Alder cycloadditions (thermal, Lewis acid-catalysed, arynes) and oxidations to afford a complimentary range of heteroaromatic systems.</p> <p>Whilst this methodology was successful with bromoenynamides, extension of its application to bromoenynhydrazides, with the hope of accessing a relatively unusual range of heteroaromatic structures including indazoles, cinnolines and diazepines, proved to be more problematic.</p> <p>Finally, expansion of the cascade methodology into a fully intramolecular cyclisation, enabled studies towards the synthesis of the trikentrin family of natural products to be conducted.</p> |
| first_indexed | 2024-03-07T04:49:56Z |
| format | Thesis |
| id | oxford-uuid:d49aad2d-65ce-4af1-acda-e90921d34a1a |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T04:49:56Z |
| publishDate | 2013 |
| record_format | dspace |
| spelling | oxford-uuid:d49aad2d-65ce-4af1-acda-e90921d34a1a2022-03-27T08:19:50ZPalladium-catalysed cyclisations of bromoenynamides in the synthesis and applications of amidodienesThesishttp://purl.org/coar/resource_type/c_db06uuid:d49aad2d-65ce-4af1-acda-e90921d34a1aChemistry & allied sciencesOrganic chemistryOrganic synthesisCatalysisEnglishOxford University Research Archive - Valet2013Greenaway, RAnderson, E<p>The aim of this work was to investigate palladium-catalysed cyclisations of bromoenynamides in the synthesis of amidodienes, which on further reaction or oxidation can lead to a diverse range of heteroaromatic systems.</p> <p>Building upon work within the Anderson group on the palladium-catalysed cyclisations of bromoenynes, we have been able to successfully apply a palladium-catalysed carbopalladation/Stille coupling/electrocyclisation cascade to bromoenynamides and then further develop this to incorporate a Suzuki coupling, leading to bicyclic amidodienes which can undergo selective oxidation to a range of heteroaromatics including indolines, indoles, tetrahydroquinolines and benzazepines.</p> <p>During the investigations into the cascade cyclisation, a reductive cyclisation was discovered which enabled access to a range of monocyclic amidodienes. These could subsequently be subjected to a series of Diels-Alder cycloadditions (thermal, Lewis acid-catalysed, arynes) and oxidations to afford a complimentary range of heteroaromatic systems.</p> <p>Whilst this methodology was successful with bromoenynamides, extension of its application to bromoenynhydrazides, with the hope of accessing a relatively unusual range of heteroaromatic structures including indazoles, cinnolines and diazepines, proved to be more problematic.</p> <p>Finally, expansion of the cascade methodology into a fully intramolecular cyclisation, enabled studies towards the synthesis of the trikentrin family of natural products to be conducted.</p> |
| spellingShingle | Chemistry & allied sciences Organic chemistry Organic synthesis Catalysis Greenaway, R Palladium-catalysed cyclisations of bromoenynamides in the synthesis and applications of amidodienes |
| title | Palladium-catalysed cyclisations of bromoenynamides in the synthesis and applications of amidodienes |
| title_full | Palladium-catalysed cyclisations of bromoenynamides in the synthesis and applications of amidodienes |
| title_fullStr | Palladium-catalysed cyclisations of bromoenynamides in the synthesis and applications of amidodienes |
| title_full_unstemmed | Palladium-catalysed cyclisations of bromoenynamides in the synthesis and applications of amidodienes |
| title_short | Palladium-catalysed cyclisations of bromoenynamides in the synthesis and applications of amidodienes |
| title_sort | palladium catalysed cyclisations of bromoenynamides in the synthesis and applications of amidodienes |
| topic | Chemistry & allied sciences Organic chemistry Organic synthesis Catalysis |
| work_keys_str_mv | AT greenawayr palladiumcatalysedcyclisationsofbromoenynamidesinthesynthesisandapplicationsofamidodienes |