dc.contributor.author |
Brimble, Margaret |
en |
dc.contributor.author |
Bryant, Christina |
en |
dc.date.accessioned |
2011-09-19T21:13:16Z |
en |
dc.date.issued |
2007 |
en |
dc.identifier.citation |
Org Biomol Chem 5(17):2858-2866 07 Sep 2007 |
en |
dc.identifier.issn |
1477-0520 |
en |
dc.identifier.uri |
http://hdl.handle.net/2292/8131 |
en |
dc.description.abstract |
The synthesis of the spiroacetal-containing anti-Helicobacter pylori agents (3S,2″S,5″S,7″S)-1a (ent-CJ-12,954) and (3S,2″S,5″R,7″S)-2a (ent-CJ-13,014) has been carried out based on the convergent union of a 1 : 1 mixture of heterocycle-activated spiroacetal sulfones 6 and 7 with (3S)-phthalide aldehyde 5a. The synthesis of the (3R)-diastereomers (3R,2″S,5″S,7″S)-1b and (3R,2″S,5″R,7″S)-2b was also undertaken in a similar manner by union of (3R)-phthalide aldehyde 5b with a 1 : 1 mixture of spiroacetal sulfones 6 and 7. Comparison of the 1H and 13C NMR data, optical rotations and HPLC retention times of the synthetic compounds (3S,2″S,5″S,7″S)-1a and (3S,2″S,5″R,7″S)-2a and the (3R)-diastereomers (3R,2″S,5″S,7″S)-1b and (3R,2″S,5″R,7″S)-2b, with the naturally occurring compounds, established that the synthetic isomers 1a and 2a were in fact enantiomeric to the natural products CJ-12,954 and CJ-13,014. The (2S,8S)-stereochemistry in protected dihydroxyketone 21, the precursor to the mixture of spiroacetal sulfones 6 and 7 was established via union of readily available (S)-acetylene 18 with aldehyde 17 in which the (4S)-stereochemistry was established via asymmetric allylation. Deprotection and cyclization of protected dihydroxyketone 21 afforded an inseparable 1 : 1 mixture of spiroacetal alcohols 24 and 25 that were converted into a 1 : 1 inseparable mixture of spiroacetal sulfones 6 and 7. Phthalide-aldehyde 3a was prepared via intramolecular acylation of bromocarbamate 11 in which the (3S)-stereochemistry was established via asymmetric CBS reduction of ketone 8. |
en |
dc.language |
EN |
en |
dc.publisher |
ROYAL SOC CHEMISTRY |
en |
dc.relation.ispartofseries |
Organic & Biomolecular Chemistry |
en |
dc.rights |
Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. Previously published items are made available in accordance with the copyright policy of the publisher. Details obtained from http://www.sherpa.ac.uk/romeo/issn/1477-0520/ |
en |
dc.rights.uri |
https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm |
en |
dc.subject |
(+)-SPIROLAXINE METHYL-ETHER |
en |
dc.subject |
MODIFIED JULIA OLEFINATION |
en |
dc.subject |
CARBONYL-COMPOUNDS |
en |
dc.subject |
SULFONES |
en |
dc.subject |
STEREOCHEMISTRY |
en |
dc.subject |
SPOROTRICALE |
en |
dc.subject |
CONDENSATION |
en |
dc.subject |
SPIROLAXINE |
en |
dc.subject |
DERIVATIVES |
en |
dc.subject |
METABOLITE |
en |
dc.title |
Synthesis and Assignment of the Absolute Configuration of the Anti-Helicobacter pylori Agents CJ-12,954 and CJ-13,014 |
en |
dc.type |
Journal Article |
en |
dc.identifier.doi |
10.1039/b709932k |
en |
pubs.issue |
17 |
en |
pubs.begin-page |
2858 |
en |
pubs.volume |
5 |
en |
dc.rights.holder |
Copyright: 2007 Royal Society of Chemistry |
en |
dc.identifier.pmid |
17700855 |
en |
pubs.end-page |
2866 |
en |
dc.rights.accessrights |
http://purl.org/eprint/accessRights/RestrictedAccess |
en |
pubs.subtype |
Article |
en |
pubs.elements-id |
74173 |
en |
pubs.org-id |
Science |
en |
pubs.org-id |
Chemistry |
en |
pubs.org-id |
Science Research |
en |
pubs.org-id |
Maurice Wilkins Centre (2010-2014) |
en |
pubs.record-created-at-source-date |
2010-09-01 |
en |
pubs.dimensions-id |
17700855 |
en |