The University of Southampton
University of Southampton Institutional Repository

Synthesis of cyclopentanoid derivatives via a metal-assisted (3 + 2) cycloaddition reaction

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
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 - Version of Record
Available under License University of Southampton Thesis Licence.
Download (8MB)

More information

Published date: 1980

Identifiers

Local EPrints ID: 459036
URI: http://eprints.soton.ac.uk/id/eprint/459036
PURE UUID: 0cf13feb-23b2-43b8-a1b7-d88fbfca18bd

Catalogue record

Date deposited: 04 Jul 2022 17:03
Last modified: 16 Mar 2024 18:27

Export record

Contributors

Author: Christopher Martin Exon
Thesis advisor: Ray Baker

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×