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Chiral bicyclic keto lactones: determination of the absolute configuration by the study of chiroptical properties and chemical correlation

Stoncius, S; Berg, Ulf LU and Butkus, E (2004) In Tetrahedron: Asymmetry 15(15). p.2405-2413
Abstract
Chiral bifunctional oxabicyclodecanediones (keto lactones) were synthesized from the corresponding bicyclo[3.3.1]nonane diones 1-5 by employing a regioselective Baeyer-Villiger oxidation. Enantiomers with high enantiomeric excess were obtained by chiral HPLC enantiomer separation on microcrystalline, triacetylcellulose column. Circular dichroism spectra of molecules containing two chromophores, namely a carbonyl and lactone in one molecule, were studied. The conformational analysis was performed with the aim to apply the octant and lactone sector rules for the determination of the absolute configuration. Ab initio and molecular mechanics calculations revealed that for all compounds investigated a single conformer, that is c-tb for 1a-3a... (More)
Chiral bifunctional oxabicyclodecanediones (keto lactones) were synthesized from the corresponding bicyclo[3.3.1]nonane diones 1-5 by employing a regioselective Baeyer-Villiger oxidation. Enantiomers with high enantiomeric excess were obtained by chiral HPLC enantiomer separation on microcrystalline, triacetylcellulose column. Circular dichroism spectra of molecules containing two chromophores, namely a carbonyl and lactone in one molecule, were studied. The conformational analysis was performed with the aim to apply the octant and lactone sector rules for the determination of the absolute configuration. Ab initio and molecular mechanics calculations revealed that for all compounds investigated a single conformer, that is c-tb for 1a-3a and 1b-2b, and c-tc for 4a, tc-tc for 5a is prevalent in the gas phase at room temperature. The applicability and limitations of the semi-empirical rules was demonstrated. The enantiospecific synthesis of enantiomerically enriched keto lactones 1-2a and 1b-2b from the corresponding enantiomeric ketones unambiguously led to the final proof of the absolute configurations. (C) 2004 Elsevier Ltd. All rights reserved. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Tetrahedron: Asymmetry
volume
15
issue
15
pages
2405 - 2413
publisher
Elsevier
external identifiers
  • wos:000223360500014
  • scopus:4143096247
ISSN
0957-4166
DOI
10.1016/j.tetasy.2004.06.018
language
English
LU publication?
yes
id
35743372-d41f-4e5d-b712-ac756eeb2f57 (old id 139433)
date added to LUP
2007-07-10 14:37:00
date last changed
2017-01-01 07:28:36
@article{35743372-d41f-4e5d-b712-ac756eeb2f57,
  abstract     = {Chiral bifunctional oxabicyclodecanediones (keto lactones) were synthesized from the corresponding bicyclo[3.3.1]nonane diones 1-5 by employing a regioselective Baeyer-Villiger oxidation. Enantiomers with high enantiomeric excess were obtained by chiral HPLC enantiomer separation on microcrystalline, triacetylcellulose column. Circular dichroism spectra of molecules containing two chromophores, namely a carbonyl and lactone in one molecule, were studied. The conformational analysis was performed with the aim to apply the octant and lactone sector rules for the determination of the absolute configuration. Ab initio and molecular mechanics calculations revealed that for all compounds investigated a single conformer, that is c-tb for 1a-3a and 1b-2b, and c-tc for 4a, tc-tc for 5a is prevalent in the gas phase at room temperature. The applicability and limitations of the semi-empirical rules was demonstrated. The enantiospecific synthesis of enantiomerically enriched keto lactones 1-2a and 1b-2b from the corresponding enantiomeric ketones unambiguously led to the final proof of the absolute configurations. (C) 2004 Elsevier Ltd. All rights reserved.},
  author       = {Stoncius, S and Berg, Ulf and Butkus, E},
  issn         = {0957-4166},
  language     = {eng},
  number       = {15},
  pages        = {2405--2413},
  publisher    = {Elsevier},
  series       = {Tetrahedron: Asymmetry},
  title        = {Chiral bicyclic keto lactones: determination of the absolute configuration by the study of chiroptical properties and chemical correlation},
  url          = {http://dx.doi.org/10.1016/j.tetasy.2004.06.018},
  volume       = {15},
  year         = {2004},
}