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The synthesis and characterization of all diastereomers of a linear symmetrically fused tris-Troger's base analogue: New chiral cleft compounds

Artacho Ruiz, Josep LU ; Nilsson, Patrik LU ; Bergquist, Karl-Erik LU ; Wendt, Ola LU and Wärnmark, Kenneth LU (2006) In Chemistry: A European Journal 12(10). p.2692-2701
Abstract
The synthesis and characterization of all diastereomers of a linear symmetrically fused tris-Troger's base analogue are described. The diastereomers are unambiguously assigned as syn-anti 1a, anti-anti 1b, and syn-syn 1c isomers, by using X-ray diffraction analysis and NMR spectroscopy. For the first time, the anti-anti and the syn-syn diastereomers of a linear symmetrically fused tris-Troger's base analogue have been synthesized. Molecules 1a and 1c are new cleft compounds and analysis of compound 1a in the solid state shows inclusion of one molecule of CH2Cl2 in the larger aromatic cleft, whereas in isomer 1c disordered solvent molecules are trapped in the extended aromatic cleft. Furthermore, in the solid state, isomer 1c forms infinite... (More)
The synthesis and characterization of all diastereomers of a linear symmetrically fused tris-Troger's base analogue are described. The diastereomers are unambiguously assigned as syn-anti 1a, anti-anti 1b, and syn-syn 1c isomers, by using X-ray diffraction analysis and NMR spectroscopy. For the first time, the anti-anti and the syn-syn diastereomers of a linear symmetrically fused tris-Troger's base analogue have been synthesized. Molecules 1a and 1c are new cleft compounds and analysis of compound 1a in the solid state shows inclusion of one molecule of CH2Cl2 in the larger aromatic cleft, whereas in isomer 1c disordered solvent molecules are trapped in the extended aromatic cleft. Furthermore, in the solid state, isomer 1c forms infinite open channels along one of the crystallographic axes and perpendicular to this axis there are infinitely extending "wedged-ravines". Importantly, each of the diastereomers 1a-c is resistant to inversion at the stereogenic nitrogen atoms under strongly and weakly acidic conditions in the range from room temperature (RT) to 95 degrees C. This observed configurational stability at the stereogenic nitrogens of 1a-c is unique for analogues of Troger's base in general to date. Finally, the ratio of cleft compounds 1a and 1c significantly increased relative to cavity compound 1b when ammonium chloride was used as an additive in the Troger's base condensation to 1a-c suggesting a templating effect of the ammonium ion. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
base, X-ray diffraction, Troger's, isomerization, inclusion compounds, chirality, cleft compound
in
Chemistry: A European Journal
volume
12
issue
10
pages
2692 - 2701
publisher
Wiley Online Library
external identifiers
  • wos:000236483400004
  • pmid:16429475
  • scopus:33645323769
ISSN
1521-3765
DOI
10.1002/chem.200501174
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240), Department of Chemistry (011001220)
id
879f22b3-c6fe-4eac-958c-484427147060 (old id 414918)
date added to LUP
2016-04-01 15:35:43
date last changed
2020-02-12 07:18:20
@article{879f22b3-c6fe-4eac-958c-484427147060,
  abstract     = {The synthesis and characterization of all diastereomers of a linear symmetrically fused tris-Troger's base analogue are described. The diastereomers are unambiguously assigned as syn-anti 1a, anti-anti 1b, and syn-syn 1c isomers, by using X-ray diffraction analysis and NMR spectroscopy. For the first time, the anti-anti and the syn-syn diastereomers of a linear symmetrically fused tris-Troger's base analogue have been synthesized. Molecules 1a and 1c are new cleft compounds and analysis of compound 1a in the solid state shows inclusion of one molecule of CH2Cl2 in the larger aromatic cleft, whereas in isomer 1c disordered solvent molecules are trapped in the extended aromatic cleft. Furthermore, in the solid state, isomer 1c forms infinite open channels along one of the crystallographic axes and perpendicular to this axis there are infinitely extending "wedged-ravines". Importantly, each of the diastereomers 1a-c is resistant to inversion at the stereogenic nitrogen atoms under strongly and weakly acidic conditions in the range from room temperature (RT) to 95 degrees C. This observed configurational stability at the stereogenic nitrogens of 1a-c is unique for analogues of Troger's base in general to date. Finally, the ratio of cleft compounds 1a and 1c significantly increased relative to cavity compound 1b when ammonium chloride was used as an additive in the Troger's base condensation to 1a-c suggesting a templating effect of the ammonium ion.},
  author       = {Artacho Ruiz, Josep and Nilsson, Patrik and Bergquist, Karl-Erik and Wendt, Ola and Wärnmark, Kenneth},
  issn         = {1521-3765},
  language     = {eng},
  number       = {10},
  pages        = {2692--2701},
  publisher    = {Wiley Online Library},
  series       = {Chemistry: A European Journal},
  title        = {The synthesis and characterization of all diastereomers of a linear symmetrically fused tris-Troger's base analogue: New chiral cleft compounds},
  url          = {http://dx.doi.org/10.1002/chem.200501174},
  doi          = {10.1002/chem.200501174},
  volume       = {12},
  year         = {2006},
}