The synthesis and reactivity of titanium metallacycles
The synthesis and reactivity of titanium metallacycles
The intramolecular addition of titanocene vinylidene complexes (formed by dechloro-dimethylalumination of 1-dimethylalumino-1-(chlorodicyclopentadienyltitana)-alkenes to unactivated alkenes and alkynes is described. This reaction affords bicyclic titanacyclobutanes and titanacyclobutenes, which can be functionalised to a variety of organic products. The intermolecular addition of titanocene vinylidene complexes to unactivated alkynes similarly affords titanacyclobutenes which undergo an insertion-rearrangement reaction with tert-butyl isocyanide to give a hitherto unknown class of compounds, the allenyl ketenimines. Hept-1-en-7-yne has been carbometallated with a series of titanocene alkyl chlorides to give bicyclic titanacyclobutanes. These have been carbonylated in situ to afford bicyclic hydroxy-ketones.
University of Southampton
1992
Dennehy, Robert Daniel
(1992)
The synthesis and reactivity of titanium metallacycles.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The intramolecular addition of titanocene vinylidene complexes (formed by dechloro-dimethylalumination of 1-dimethylalumino-1-(chlorodicyclopentadienyltitana)-alkenes to unactivated alkenes and alkynes is described. This reaction affords bicyclic titanacyclobutanes and titanacyclobutenes, which can be functionalised to a variety of organic products. The intermolecular addition of titanocene vinylidene complexes to unactivated alkynes similarly affords titanacyclobutenes which undergo an insertion-rearrangement reaction with tert-butyl isocyanide to give a hitherto unknown class of compounds, the allenyl ketenimines. Hept-1-en-7-yne has been carbometallated with a series of titanocene alkyl chlorides to give bicyclic titanacyclobutanes. These have been carbonylated in situ to afford bicyclic hydroxy-ketones.
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Published date: 1992
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Local EPrints ID: 461051
URI: http://eprints.soton.ac.uk/id/eprint/461051
PURE UUID: 4d90ea77-e014-4019-8d4c-13cf81aff730
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Date deposited: 04 Jul 2022 18:34
Last modified: 04 Jul 2022 18:34
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Author:
Robert Daniel Dennehy
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