Thesis-1996-Ferris.pdf (2.78 MB)
Rhodium carboxylates as catalysts for carbenoid transformations
thesis
posted on 2018-04-17, 11:10 authored by Leigh FerrisChapter One reviews the literature, discussing the application of
metallocarbenoids in asymmetric synthesis. This introduction is mainly
concerned with asymmetric carbon-carbon and carbon-heteroatom bond
forming reactions and pays particular attention to the levels of
stereoselectivity that have been achieved.
Chapter Two discusses the use of novel homochiral rhodium(II)
carboxylates to effect asymmetric induction in a range of carbenoid
transformations. The preparation of these novel rhodium(II) carboxylates is
discussed, together with their application in asymmetric catalysis. The work
presented is particularly concerned with the insertion of rhodium carbenoids
into the heteroatom-hydrogen bond of alcohols, thiols, amines and silanes to
prepare enantiomerically enriched a-substituted esters.
Chapter Three discusses the generation of oxygen and sulfur ylides followed
by a [2,3] sigmatropic rearrangement to generate enantiomerically enriched
esters containing a quaternary chiral centre. Asymmetric cyclopropanations
and carbon-hydrogen insertion reactions are also discussed.
Chapter Four examines the use of diazo phosphonoacetate in organic
synthesis. The work has concentrated on the preparation of N-substituted
aminophosphonoacetates, by the insertion reactions of anilines, amides and
carbamates. These compounds have then been manipulated to prepare a
series of amino esters and peptides.
Funding
SERC and SmithKline Beecham plc (CASE grant).
History
School
- Science
Department
- Chemistry
Publisher
© Leigh FerrisPublisher 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