Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.485415
Title: Allylic amine synthesis via sulfimide rearrangement
Author: Challinor, Lee
ISNI:       0000 0001 3525 9491
Awarding Body: Imperial College London
Current Institution: Imperial College London
Date of Award: 2008
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Abstract:
This thesis reports the development of a novel asymmetric route towards a variety of NBoc protected allylic amines. This was achieved by creating an organocatalytic asymmetric transformation of aldehydes into a diverse range of allylic sulfides, and then applying a [2,3]-sigmatropic rearrangement with chirality transfer to afford five target motifs that will be discussed in individual chapters. Chapter One. introduces the general topi:along with supporting references. Chapter Two focuses on allylic amines and a [2,3]-sigmatropic rearrangement as a method ofasymmetric C-N bond construction via sulfimidation. The use of an oxaziridine reagent as an electrophilic source ofNBoc to induce rearrangement of prochiral allylic sulfides is then discussed prior to optimisation of a chemoselective version utilising chiral substrates..The chirality transfer is addressed in light of contradictory evidence, and confirmed as complete with simple aliphatic allylic sulfides and several unexplored substrates. Chapter Three highlights vinyl glycines and the development of an organocatalytic preparation of chiral substrates which had previously only been available from a limited chiral pool. Both (E) and (2) allylic sulfides were selectively prepared and the creation of a one-pot amination-rearrangement/N-S- bond cleavage sequence afforded both optical isomers of the target compounds with a variety of y-substituents. Chapter Four focuses on quaternary substituted vinyl glycines which were prepared with an array of a- and y-substituents by optimising the asymmetric organocatalytic preparation of geometrically enriched tri-substituted allylic sulfides through variation ofthe aldehyde and olefinating reagent respectively. Chapter Five discuses allylic afluoro aminoacids and their inherent instability. Chapter Six covers allylic a-aminophosphonates where the organocatalytic preparation of chiral vinylic phosphonates was achieved along with their amination-rearrangement, but the chirality transfer remains to be examined. Chapter Seven concludes our findings and outlines future research. Chapter Eight provides experimental details with spectroscopic and physical data for new compounds.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.485415  DOI: Not available
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