The University of Southampton
University of Southampton Institutional Repository

Synthesis of trimethyl (2S,3R)- and (2R,3R)-[2-2H1]-homocitrates and dimethyl (2S,3R)- and (2R,3R)-[2-2H1]-homocitrate lactones: an assay for the stereochemical outcome of the reaction catalysed both by homocitrate synthase and by the Nif-V protein

Synthesis of trimethyl (2S,3R)- and (2R,3R)-[2-2H1]-homocitrates and dimethyl (2S,3R)- and (2R,3R)-[2-2H1]-homocitrate lactones: an assay for the stereochemical outcome of the reaction catalysed both by homocitrate synthase and by the Nif-V protein
Synthesis of trimethyl (2S,3R)- and (2R,3R)-[2-2H1]-homocitrates and dimethyl (2S,3R)- and (2R,3R)-[2-2H1]-homocitrate lactones: an assay for the stereochemical outcome of the reaction catalysed both by homocitrate synthase and by the Nif-V protein
Trimethyl (3R)-homocitrate 17, trimethyl (2S,3R)-[2-2H1]-homocitrate 17a and (2R,3R)-[2-2H1]-homocitrate 17b, as well as dimethyl (3R)-homocitrate lactone 18, (2S,3R)-[2-2H1]-homocitric lactone 18a and (2R,3R)-[2-2H1]-homocitric lactone 18b have been synthesised. D-quinic acid 12 was used as the source of the (3R)-centre in the unlabelled target compounds 17 and 18. (2)-Shikimic acid 19 and the (2)-[2-2H]-shikimic acid derivative 32 respectively were used in the synthesis of the labelled compounds. In the latter syntheses, Sharpless directed epoxidation of the olefin in the 5-deoxy ester diols 23 and 35 ensured a reaction from the same face as the allylic and homoallylic alcohols, and the reduction of the protected epoxides 25 and 37 ensured that the label was introduced in a stereoselective manner. The 1H NMR spectra of the labelled products present an assay for the stereochemistry of the biological reactions catalysed by homocitrate synthase and by the protein from the nifV gene.
bacterial proteins, metabolism catalysis lactones, chemical synthesis/chemistry, metabolism lysine/metabolism magnetic resonance spectroscopy methylation molecular structure oxo-acid-lyases, metabolism stereoisomerism tricarboxylic acids, metabolism
1477-0520
569-580
Tavassoli, Ali
d561cf8f-2669-46b5-b6e1-2016c85d63b2
Duffy, James E.S.
158057e8-e088-4313-9159-b2ebfb57a97e
Young, Douglas W.
e205a9a7-1851-4b08-9f71-1109df35a8e2
Tavassoli, Ali
d561cf8f-2669-46b5-b6e1-2016c85d63b2
Duffy, James E.S.
158057e8-e088-4313-9159-b2ebfb57a97e
Young, Douglas W.
e205a9a7-1851-4b08-9f71-1109df35a8e2

Tavassoli, Ali, Duffy, James E.S. and Young, Douglas W. (2006) Synthesis of trimethyl (2S,3R)- and (2R,3R)-[2-2H1]-homocitrates and dimethyl (2S,3R)- and (2R,3R)-[2-2H1]-homocitrate lactones: an assay for the stereochemical outcome of the reaction catalysed both by homocitrate synthase and by the Nif-V protein. Organic & Biomolecular Chemistry, 4 (3), 569-580. (doi:10.1039/b515937g).

Record type: Article

Abstract

Trimethyl (3R)-homocitrate 17, trimethyl (2S,3R)-[2-2H1]-homocitrate 17a and (2R,3R)-[2-2H1]-homocitrate 17b, as well as dimethyl (3R)-homocitrate lactone 18, (2S,3R)-[2-2H1]-homocitric lactone 18a and (2R,3R)-[2-2H1]-homocitric lactone 18b have been synthesised. D-quinic acid 12 was used as the source of the (3R)-centre in the unlabelled target compounds 17 and 18. (2)-Shikimic acid 19 and the (2)-[2-2H]-shikimic acid derivative 32 respectively were used in the synthesis of the labelled compounds. In the latter syntheses, Sharpless directed epoxidation of the olefin in the 5-deoxy ester diols 23 and 35 ensured a reaction from the same face as the allylic and homoallylic alcohols, and the reduction of the protected epoxides 25 and 37 ensured that the label was introduced in a stereoselective manner. The 1H NMR spectra of the labelled products present an assay for the stereochemistry of the biological reactions catalysed by homocitrate synthase and by the protein from the nifV gene.

Full text not available from this repository.

More information

Published date: 2006
Keywords: bacterial proteins, metabolism catalysis lactones, chemical synthesis/chemistry, metabolism lysine/metabolism magnetic resonance spectroscopy methylation molecular structure oxo-acid-lyases, metabolism stereoisomerism tricarboxylic acids, metabolism

Identifiers

Local EPrints ID: 45302
URI: http://eprints.soton.ac.uk/id/eprint/45302
ISSN: 1477-0520
PURE UUID: 5257e1c0-dd86-4591-b8d3-7e2eaa117fbf
ORCID for Ali Tavassoli: ORCID iD orcid.org/0000-0002-7420-5063

Catalogue record

Date deposited: 20 Mar 2007
Last modified: 20 Jul 2019 00:54

Export record

Altmetrics

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.

×