Intramolecular processes of nickel and phosphorus intermediates
Intramolecular processes of nickel and phosphorus intermediates
The intramolecular cyclisation of a a-allylnickel halide complex with an alkyl halide has been investigated. In studies directed towards the synthesis of lactones the nickel reactions of (Z)-4-(l-br.bmobut-2-enyl) 3-firomopropionate and (Z)-5-(l-bromopent-3-enyl) bromoacetate have been investigated. Further model reactions have included the attempted cyclisation of (Z)-l,8-dibromooct-2-ene and (Z)-1,6-dibromohex-2-ene. Conditions for the reaction of the 7r-allylnickel bromide complex of (Z)-1,B-dibromooctene with iodobenzene to give 8-bromo-lphenyloct-2-ene have been developed. An approach to the synthesis of the macrolides (±)-phoracantholide 3 and (t)-recifieolide has been investigated. The stereospecific synthesis of germacrene D, which acts as an attractant to cockroaches, has been undertaken. The key reaction employed in this-synthesis was an intramolecular Wittig reaction, to construct the ten-membered germacranoid ring. Reaction of 1-tetrahydropyranyloxy-3- [2-(1,3-dith7ane)]propane with (3R)-6-(1,3-dioxolan-2-yl)-3-(1-methylethyl)heptan-l-al, followed by functional group interconversion gave the required Wittig cyclisation precursor. Attempted cyclisation under the conditions described in the literature gave none of the required cyclic products. Examination of the intermolecular reaction between heptan-2-one and n-pentyltriphenylphosphonium bromide gave conditions under which the Wittig reaction products, (Z-)- and (E)-6-methyl-5-undecene, could be isolated in high yield. When the reaction conditions, developed in the model studies, were employed in the cyclisation reaction, again no cyclic products could be isolated. The synthesis of the model cyclisation precursor, 10-oxoundecanyltriphenylphosphonium bromide, has been achieved in high yield and its reactions have been studied. Although no cyclic products were isolated, some evidence was obtained for intermolecular reaction.
University of Southampton
1982
Cumming, Stephen Andrew
(1982)
Intramolecular processes of nickel and phosphorus intermediates.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The intramolecular cyclisation of a a-allylnickel halide complex with an alkyl halide has been investigated. In studies directed towards the synthesis of lactones the nickel reactions of (Z)-4-(l-br.bmobut-2-enyl) 3-firomopropionate and (Z)-5-(l-bromopent-3-enyl) bromoacetate have been investigated. Further model reactions have included the attempted cyclisation of (Z)-l,8-dibromooct-2-ene and (Z)-1,6-dibromohex-2-ene. Conditions for the reaction of the 7r-allylnickel bromide complex of (Z)-1,B-dibromooctene with iodobenzene to give 8-bromo-lphenyloct-2-ene have been developed. An approach to the synthesis of the macrolides (±)-phoracantholide 3 and (t)-recifieolide has been investigated. The stereospecific synthesis of germacrene D, which acts as an attractant to cockroaches, has been undertaken. The key reaction employed in this-synthesis was an intramolecular Wittig reaction, to construct the ten-membered germacranoid ring. Reaction of 1-tetrahydropyranyloxy-3- [2-(1,3-dith7ane)]propane with (3R)-6-(1,3-dioxolan-2-yl)-3-(1-methylethyl)heptan-l-al, followed by functional group interconversion gave the required Wittig cyclisation precursor. Attempted cyclisation under the conditions described in the literature gave none of the required cyclic products. Examination of the intermolecular reaction between heptan-2-one and n-pentyltriphenylphosphonium bromide gave conditions under which the Wittig reaction products, (Z-)- and (E)-6-methyl-5-undecene, could be isolated in high yield. When the reaction conditions, developed in the model studies, were employed in the cyclisation reaction, again no cyclic products could be isolated. The synthesis of the model cyclisation precursor, 10-oxoundecanyltriphenylphosphonium bromide, has been achieved in high yield and its reactions have been studied. Although no cyclic products were isolated, some evidence was obtained for intermolecular reaction.
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Published date: 1982
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Local EPrints ID: 460294
URI: http://eprints.soton.ac.uk/id/eprint/460294
PURE UUID: 01d4bdee-07d0-48fd-bfd9-5e414f6d7955
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Date deposited: 04 Jul 2022 18:18
Last modified: 04 Jul 2022 18:18
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Author:
Stephen Andrew Cumming
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