{"id":{"repo_id":"auckland-ms","oai_identifier":"oai:researchspace.auckland.ac.nz:2292/20656"},"canonical_url":"https://search.dev.ndltd.org/etd/auckland-ms/oai:researchspace.auckland.ac.nz:2292/20656","repository":{"repo_id":"auckland-ms","name":"University of Auckland","base_url":"https://researchspace.auckland.ac.nz/server/oai/request"},"display":{"title":"Developments in Acyl-Claisen Rearrangements and Application to Synthesis","abstract":"The acyl-Claisen rearrangement is a powerful [3,3]-sigmatropic rearrangement of an allylic amine and an acyl chloride derived ketene. The α,β-substituted-γ,δ-olefinic amide 32 derived from this rearrangement has been demonstrated to be a powerful scaffold for elaboration via a number of routes. This thesis describes the extension of acyl-Claisen rearrangement methodology to produce di-aromatic amides where previously only mono-aromatic amides had been produced. A screen of Lewis acids was carried out in an attempt to optimise rearrangement conditions and a variety of aromatic substrates of varying substitution were utilised. Elaboration of diaromatic amides was then carried out to produce novel tetraphenyl-tetrahydrofuran 109c and progress was made towards the synthesis of resveratrol dimer tricuspidatol A 109b. Finally the synthesis of magnosalicin 112 was completed via mono-aromatic amide 32m. The acyl-Claisen rearrangement methodology was further extended in an attempt to produce an asymmetric variant. Preparation of 3-substituted morpholines 181a-g from amino alcohols was carried out and subsequent allylation of these morpholines provided chiral substrates for the acyl-Claisen rearrangement. Rearrangement of many of these chiral allylic morpholines 182a-h/183a-h proved successful and analysis of the pseudoenantiomeric amides produced was carried out by chiral HPLC. Diastereoselectivity ranged from 50:50 to 92:8, although yields also varied widely (14 – 98%). Choosing the most robust rearrangement from this series we carried out a screen of acyl chlorides, establishing a wide range of suitable substituents.","abstract_html":"The acyl-Claisen rearrangement is a powerful [3,3]-sigmatropic rearrangement of an allylic amine and an acyl chloride derived ketene. The α,β-substituted-γ,δ-olefinic amide 32 derived from this rearrangement has been demonstrated to be a powerful scaffold for elaboration via a number of routes. This thesis describes the extension of acyl-Claisen rearrangement methodology to produce di-aromatic amides where previously only mono-aromatic amides had been produced. A screen of Lewis acids was carried out in an attempt to optimise rearrangement conditions and a variety of aromatic substrates of varying substitution were utilised. Elaboration of diaromatic amides was then carried out to produce novel tetraphenyl-tetrahydrofuran 109c and progress was made towards the synthesis of resveratrol dimer tricuspidatol A 109b. Finally the synthesis of magnosalicin 112 was completed via mono-aromatic amide 32m. The acyl-Claisen rearrangement methodology was further extended in an attempt to produce an asymmetric variant. Preparation of 3-substituted morpholines 181a-g from amino alcohols was carried out and subsequent allylation of these morpholines provided chiral substrates for the acyl-Claisen rearrangement. Rearrangement of many of these chiral allylic morpholines 182a-h/183a-h proved successful and analysis of the pseudoenantiomeric amides produced was carried out by chiral HPLC. Diastereoselectivity ranged from 50:50 to 92:8, although yields also varied widely (14 – 98%). Choosing the most robust rearrangement from this series we carried out a screen of acyl chlorides, establishing a wide range of suitable substituents.","abstract_has_math":false,"creators":["Dickson, Benjamin"],"institution":"ResearchSpace@Auckland","degree_name":"PhD","degree_level":"Doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Barker, D"],"committee_chairs":[],"committee_members":[],"year":2013,"date_issued":"2013-07-22","date_published":"2013-07-22","updated_at":"2026-07-24T01:04:52Z","subjects":[],"languages":[],"rights":["Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. 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A screen of Lewis acids was carried out in an attempt to optimise rearrangement conditions and a variety of aromatic substrates of varying substitution were utilised. Elaboration of diaromatic amides was then carried out to produce novel tetraphenyl-tetrahydrofuran 109c and progress was made towards the synthesis of resveratrol dimer tricuspidatol A 109b. Finally the synthesis of magnosalicin 112 was completed via mono-aromatic amide 32m. The acyl-Claisen rearrangement methodology was further extended in an attempt to produce an asymmetric variant. Preparation of 3-substituted morpholines 181a-g from amino alcohols was carried out and subsequent allylation of these morpholines provided chiral substrates for the acyl-Claisen rearrangement. Rearrangement of many of these chiral allylic morpholines 182a-h/183a-h proved successful and analysis of the pseudoenantiomeric amides produced was carried out by chiral HPLC. Diastereoselectivity ranged from 50:50 to 92:8, although yields also varied widely (14 – 98%). Choosing the most robust rearrangement from this series we carried out a screen of acyl chlorides, establishing a wide range of suitable substituents."]},{"key":"dc:title","label":"Title","values":["Developments in Acyl-Claisen Rearrangements and Application to Synthesis"]}]}],"canonical_facts":{"dc:contributor.advisor":["Barker, D"],"dc:creator":["Dickson, Benjamin"],"dc:date.accessioned":["2013-08-01T21:57:57Z"],"dc:date.issued":["2013-07-22"],"dc:description.abstract":["The acyl-Claisen rearrangement is a powerful [3,3]-sigmatropic rearrangement of an allylic amine and an acyl chloride derived ketene. The α,β-substituted-γ,δ-olefinic amide 32 derived from this rearrangement has been demonstrated to be a powerful scaffold for elaboration via a number of routes. This thesis describes the extension of acyl-Claisen rearrangement methodology to produce di-aromatic amides where previously only mono-aromatic amides had been produced. A screen of Lewis acids was carried out in an attempt to optimise rearrangement conditions and a variety of aromatic substrates of varying substitution were utilised. Elaboration of diaromatic amides was then carried out to produce novel tetraphenyl-tetrahydrofuran 109c and progress was made towards the synthesis of resveratrol dimer tricuspidatol A 109b. Finally the synthesis of magnosalicin 112 was completed via mono-aromatic amide 32m. The acyl-Claisen rearrangement methodology was further extended in an attempt to produce an asymmetric variant. Preparation of 3-substituted morpholines 181a-g from amino alcohols was carried out and subsequent allylation of these morpholines provided chiral substrates for the acyl-Claisen rearrangement. Rearrangement of many of these chiral allylic morpholines 182a-h/183a-h proved successful and analysis of the pseudoenantiomeric amides produced was carried out by chiral HPLC. Diastereoselectivity ranged from 50:50 to 92:8, although yields also varied widely (14 – 98%). Choosing the most robust rearrangement from this series we carried out a screen of acyl chlorides, establishing a wide range of suitable substituents."],"dc:identifier.uri":["https://hdl.handle.net/2292/20656"],"dc:publisher":["ResearchSpace@Auckland"],"dc:rights":["Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. Previously published items are made available in accordance with the copyright policy of the publisher."],"dc:rights.uri":["https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm"],"dc:title":["Developments in Acyl-Claisen Rearrangements and Application to Synthesis"],"dc:type":["Thesis"],"thesis:degree_level":["Doctoral"],"thesis:degree_name":["PhD"],"thesis:institution_name":["The University of Auckland"]},"updated_at":"2026-07-24T01:04:52Z"}