Synthesis of cyclopentanoid derivatives via a metal-assisted (3 + 2) cycloaddition reaction
Synthesis of cyclopentanoid derivatives via a metal-assisted (3 + 2) cycloaddition reaction
The reactions of (n'-allyl)Fp complexes with electron-deficient olefins and acetylenes, and the replacement of the iron complex of the cyclopentyl-Fp complexes thus formed with an organic functionality have been investigated. Cyclic adducts were the exclusive products from the reaction of the simple (n'-allyl)Fp complex (20a) and the (n'-3-methoxyallyl)Fp complex (28) with olefinic species, whereas linear adducts (arising from a H-transfer process), as well as cyclic products, were isolated from the reaction of the (n'-2-methoxyallyl)Fp complex (66) with unsaturated moieties. The reactivity of the 2-methoxyallyl complex was observed to be substantially greater than that of either (20a) or (28).
Ammonium ceric nitrate oxidation of alcoholic solutions of cyclopentyl-Fp and 2-methoxycyclopentyl-Fp complexes led to the replacement of the Fp group with a carboxylic ester functionality. Similar treatment of 1methoxycyclopentyl-Fp complexes gave a mixture of ketalic and olefinic derivatives. Reaction of cyclopentyl-Fp complexes with gaseous hydrochloric acid afforded products resulting from a ring-opening process, as well as cyclic adducts arising from the replacement of the Fp complex with a proton. Analogous treatment of 2-methoxycyclopentyl-Fp complexes resulted in the elimination of FpOMe to give cyclopentene derivatives. A mixture of brominated and olefinic derivatives were isolated from the reaction of cyclopentyl-Fp complexes with N-bromopyridinium bromide.
A preliminary study of the possible uses of the metal assisted (3+2) cycloaddition reaction in the synthesis of a variety of cyclopentanoid natural products was also performed.
University of Southampton
Exon, Christopher Martin
416d3349-6113-48b1-afe8-3f8fa5660a57
1980
Exon, Christopher Martin
416d3349-6113-48b1-afe8-3f8fa5660a57
Baker, Ray
d98b9a63-b284-44de-b3c5-f837e845ae96
Exon, Christopher Martin
(1980)
Synthesis of cyclopentanoid derivatives via a metal-assisted (3 + 2) cycloaddition reaction.
University of Southampton, Doctoral Thesis, 198pp.
Record type:
Thesis
(Doctoral)
Abstract
The reactions of (n'-allyl)Fp complexes with electron-deficient olefins and acetylenes, and the replacement of the iron complex of the cyclopentyl-Fp complexes thus formed with an organic functionality have been investigated. Cyclic adducts were the exclusive products from the reaction of the simple (n'-allyl)Fp complex (20a) and the (n'-3-methoxyallyl)Fp complex (28) with olefinic species, whereas linear adducts (arising from a H-transfer process), as well as cyclic products, were isolated from the reaction of the (n'-2-methoxyallyl)Fp complex (66) with unsaturated moieties. The reactivity of the 2-methoxyallyl complex was observed to be substantially greater than that of either (20a) or (28).
Ammonium ceric nitrate oxidation of alcoholic solutions of cyclopentyl-Fp and 2-methoxycyclopentyl-Fp complexes led to the replacement of the Fp group with a carboxylic ester functionality. Similar treatment of 1methoxycyclopentyl-Fp complexes gave a mixture of ketalic and olefinic derivatives. Reaction of cyclopentyl-Fp complexes with gaseous hydrochloric acid afforded products resulting from a ring-opening process, as well as cyclic adducts arising from the replacement of the Fp complex with a proton. Analogous treatment of 2-methoxycyclopentyl-Fp complexes resulted in the elimination of FpOMe to give cyclopentene derivatives. A mixture of brominated and olefinic derivatives were isolated from the reaction of cyclopentyl-Fp complexes with N-bromopyridinium bromide.
A preliminary study of the possible uses of the metal assisted (3+2) cycloaddition reaction in the synthesis of a variety of cyclopentanoid natural products was also performed.
Text
Exon 1980 Thesis
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Published date: 1980
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Local EPrints ID: 459036
URI: http://eprints.soton.ac.uk/id/eprint/459036
PURE UUID: 0cf13feb-23b2-43b8-a1b7-d88fbfca18bd
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Date deposited: 04 Jul 2022 17:03
Last modified: 16 Mar 2024 18:27
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Contributors
Author:
Christopher Martin Exon
Thesis advisor:
Ray Baker
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