Synthetic applications of nitrile oxide-olefin dipolar additions
Synthetic applications of nitrile oxide-olefin dipolar additions
Reduced isoquinolines have been shown to exhibit marked analgesic activity, thus establishing themselves as worthy synthetic targets. Nitrile oxide 1,3-dipolar additions to 1-phenylthio-l,3-butadier: a gave 3-substituted-5-(2-phenylthioethen-l-yl)-2-isoxazolines, whirr on reduction afforded the corresponding amino-alcohols. Further modification gave rise to 5-amino-a,5-unsaturated aldehydes. Unfortunately, the requisite Diels-Alder reaction of these aldehydes to give precursors of reduced isoquinolines did not meet with success. However, intramolecular Diels-Alder cycloaddition of ethyl 7acrylamido-2,4-octadienoate gave the desired isoquinoline skeleton. Synthetic approaches to-the Strychnos, indole alkaloid retulinal were also carried out, centering on the preparation of a model compound, (Z)-8-ethylidine-5-formyl-2,3,3a,6,7,7a-hexahydro-3a-phenyl1,6-ethano-lH-indole. A key intramolecular nitrile oxide addition failed due to nitrile oxide dimerisation. However, an approach based on a Claisen rearrangement followed by an amine to ester cyclisation produced the desired ethanoindole framework. Studies were then directed towards the synthesis of retulinal.
University of Southampton
1983
Lathbury, David Charles
(1983)
Synthetic applications of nitrile oxide-olefin dipolar additions.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Reduced isoquinolines have been shown to exhibit marked analgesic activity, thus establishing themselves as worthy synthetic targets. Nitrile oxide 1,3-dipolar additions to 1-phenylthio-l,3-butadier: a gave 3-substituted-5-(2-phenylthioethen-l-yl)-2-isoxazolines, whirr on reduction afforded the corresponding amino-alcohols. Further modification gave rise to 5-amino-a,5-unsaturated aldehydes. Unfortunately, the requisite Diels-Alder reaction of these aldehydes to give precursors of reduced isoquinolines did not meet with success. However, intramolecular Diels-Alder cycloaddition of ethyl 7acrylamido-2,4-octadienoate gave the desired isoquinoline skeleton. Synthetic approaches to-the Strychnos, indole alkaloid retulinal were also carried out, centering on the preparation of a model compound, (Z)-8-ethylidine-5-formyl-2,3,3a,6,7,7a-hexahydro-3a-phenyl1,6-ethano-lH-indole. A key intramolecular nitrile oxide addition failed due to nitrile oxide dimerisation. However, an approach based on a Claisen rearrangement followed by an amine to ester cyclisation produced the desired ethanoindole framework. Studies were then directed towards the synthesis of retulinal.
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Published date: 1983
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Local EPrints ID: 459937
URI: http://eprints.soton.ac.uk/id/eprint/459937
PURE UUID: 313e4740-58a2-41d8-b965-f5e0f6acde88
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Date deposited: 04 Jul 2022 17:28
Last modified: 04 Jul 2022 17:28
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Author:
David Charles Lathbury
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