Synthetic applications of 1, 3- dipolar cycloadditions
Synthetic applications of 1, 3- dipolar cycloadditions
Approaches to various synthetic targets utilizing the 1,3-dipolar cycloaddition reaction to nitrile oxides and nitrones are described. An approach to the 1,6-dioxaspiro[4.5]decane system, involving cycloaddition of an unsaturated nitrile oxide to tetrahydro-2-methylenefuran, failed due to the resistance to reductive cleavage and ease of aromatization of the isoxazoline intermediate. A modified approach, using nitrone cycloaddition chemistry, was more encouraging, but not synthetically useful. The intramolecular cycloaddition of a nitrone to an acetylene was envisaged as the key step in a new route to carbapenems. A model study was undertaken. The desired cycloaddition could not be affected, but an interesting pyrrole synthesis was observed. An attempt to apply an acylative cycloaddition reaction to a synthesis of the aspidosperma alkaloid, vindoline, was undertaken. A model study confirmed the potential of the acylative cycloaddition. The projected route to vindoline was beset with difficulties and was eventually abandoned due to lack of time. Finally, a synthesis of cocaine incorporating a tandem Michael addition - nitrone 1,3-dipolar cycloaddition as the key step was attempted. The key step failed: the cause of this failure was investigated and tentatively identified.
University of Southampton
1988
Quillin, Helen Kaye
(1988)
Synthetic applications of 1, 3- dipolar cycloadditions.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
Approaches to various synthetic targets utilizing the 1,3-dipolar cycloaddition reaction to nitrile oxides and nitrones are described. An approach to the 1,6-dioxaspiro[4.5]decane system, involving cycloaddition of an unsaturated nitrile oxide to tetrahydro-2-methylenefuran, failed due to the resistance to reductive cleavage and ease of aromatization of the isoxazoline intermediate. A modified approach, using nitrone cycloaddition chemistry, was more encouraging, but not synthetically useful. The intramolecular cycloaddition of a nitrone to an acetylene was envisaged as the key step in a new route to carbapenems. A model study was undertaken. The desired cycloaddition could not be affected, but an interesting pyrrole synthesis was observed. An attempt to apply an acylative cycloaddition reaction to a synthesis of the aspidosperma alkaloid, vindoline, was undertaken. A model study confirmed the potential of the acylative cycloaddition. The projected route to vindoline was beset with difficulties and was eventually abandoned due to lack of time. Finally, a synthesis of cocaine incorporating a tandem Michael addition - nitrone 1,3-dipolar cycloaddition as the key step was attempted. The key step failed: the cause of this failure was investigated and tentatively identified.
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Published date: 1988
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Local EPrints ID: 461089
URI: http://eprints.soton.ac.uk/id/eprint/461089
PURE UUID: 2bcced48-bbb4-444f-a010-09dbbdf7a4f9
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Date deposited: 04 Jul 2022 18:35
Last modified: 04 Jul 2022 18:35
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Author:
Helen Kaye Quillin
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