The synthesis of novel zirconium complexes utilising lithium carbenoids
The synthesis of novel zirconium complexes utilising lithium carbenoids
Cyclopentandienyl zirconium complexes are becoming more prevalent in mainstream organic chemistry as they can facilitate the rapid assembly of complex organic molecules from relatively simple precursors.
Current methodology for the elaboration of these zirconium complexes is limited to reactions of zirconacyclopentanes with halogens, oxygen and some carbenoid type molecules such as carbon monoxide and aliphatic isocyanides.
The work presented within this thesis is aimed at transformations of the known zirconacyclopentanes into novel zirconacyclohexanes. To this end, a range of substituted lithium halocarbenoids are shown to cleanly insert into cyclopentyl zirconium complexes to form a number of new homologated zirconacyclohexanes.
The lithium carbenoids used for new transformations are either currently known in the primary literature, but have never previously been utilised with zirconium as the template. A number of new classes of lithium carbenoids are also developed within the thesis. And their subsequent use in the 1,2-metalate rearrangement reaction is discussed. A number of unusual side reactions and mechanisms' are proposed to help understand how some of the organic products are formed.
In addition, the actual structure of some of the new zirconium complexes is revealed with particular reference to the co-ordination modes of allyl and propargyl ligands towards the zirconium centre.
Finally a convergent and highly efficient regio- and stereo-selective synthesis of 1,4-dienes is reported.
University of Southampton
1998
Fillery, Shaun Michael
(1998)
The synthesis of novel zirconium complexes utilising lithium carbenoids.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Cyclopentandienyl zirconium complexes are becoming more prevalent in mainstream organic chemistry as they can facilitate the rapid assembly of complex organic molecules from relatively simple precursors.
Current methodology for the elaboration of these zirconium complexes is limited to reactions of zirconacyclopentanes with halogens, oxygen and some carbenoid type molecules such as carbon monoxide and aliphatic isocyanides.
The work presented within this thesis is aimed at transformations of the known zirconacyclopentanes into novel zirconacyclohexanes. To this end, a range of substituted lithium halocarbenoids are shown to cleanly insert into cyclopentyl zirconium complexes to form a number of new homologated zirconacyclohexanes.
The lithium carbenoids used for new transformations are either currently known in the primary literature, but have never previously been utilised with zirconium as the template. A number of new classes of lithium carbenoids are also developed within the thesis. And their subsequent use in the 1,2-metalate rearrangement reaction is discussed. A number of unusual side reactions and mechanisms' are proposed to help understand how some of the organic products are formed.
In addition, the actual structure of some of the new zirconium complexes is revealed with particular reference to the co-ordination modes of allyl and propargyl ligands towards the zirconium centre.
Finally a convergent and highly efficient regio- and stereo-selective synthesis of 1,4-dienes is reported.
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Published date: 1998
Identifiers
Local EPrints ID: 463532
URI: http://eprints.soton.ac.uk/id/eprint/463532
PURE UUID: 09b48268-8fc1-44e5-a775-fe469ba28934
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Date deposited: 04 Jul 2022 20:53
Last modified: 04 Jul 2022 20:53
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Author:
Shaun Michael Fillery
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