Developments in Acyl-Claisen Rearrangements and Application to Synthesis

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.

Name thesis:degree_name

PhD

Level thesis:degree_level

Doctoral

Grantor dc:publisher

ResearchSpace@Auckland

Year dc:date.issued

2013

Author dc:creator

• Dickson, Benjamin

Advisor dc:contributor.advisor

• Barker, D

Statement 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.

Licence dc:rights.uri

• https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm

Handle dc:identifier.uri

https://hdl.handle.net/2292/20656

OAI identifier oai:identifier

oai:researchspace.auckland.ac.nz:2292/20656