Thesis-2001-Baird.pdf (4.59 MB)
Development and synthetic applications of the asymmetric anionic amino-Cope rearrangement
thesis
posted on 2018-07-18, 08:13 authored by Robert D. BairdThe thermal and anionic amino-Cope rearrangement of suitably functionalised 3-amino-1,5-hexadienes
could potentially constitute a powerful tool for the stereoselective synthesis of
highly functionalised acyclic or cyclic systems. [Illustration omitted.]
Incorporation of β-aminoalcohol auxiliaries into the diene enabled high diastereoselectivity
to be obtained during the 1,2-addition of the allyl Grignard reagent to α,β-unsaturated
imines. Asymmetric anionic amino-Cope rearrangement of the diastereoisomerically pure
3-amino-1,5-diene substrates furnished the target aldehyde in good yield and with high levels
of asymmetric induction (up to 94% e.e.).
The aldehyde obtained was used as a non-racemic starting material to synthesise small
heterocycles, with high levels of diastereoselectivity in some cases, providing a high yielding
route to some important chiral building blocks. The successful formation of both
tetrahydropyrans and lactones without any apparent loss of chirality was achieved and
provided a background for investigation into the synthesis of piperidines, which could lead to
a plausible route to biologically significant aza-sugars. [Illustration omitted.]
Funding
EPSRC.
History
School
- Science
Department
- Chemistry
Publisher
© R.D. BairdPublisher statement
This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/Publication date
1996Notes
A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy at Loughborough University.Language
- en