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Synthesis, Molecular Structure, and Chiroptical Properties of Dibenzylidene Derivatives of Bicyclo[3.3.1]nonane and Brexane.

Stončius, Sigitas ; Neniškis, Algirdas ; Loganathan, Nagarajan LU and Wendt, Ola LU (2015) In Chirality 27(10). p.728-737
Abstract
Synthesis of several enantiomerically pure unsaturated bicyclo[3.3.1]nonane and related brexane (tricyclo[4.3.0.0(3,7) ]nonane) derivatives bearing exocyclic benzylidene substituents from readily available (+)-(1S,5S)-bicyclo[3.3.1]nonane-2,6-dione was accomplished. Molecular geometry and chiroptical properties of compounds with enone and styrene chromophores were studied by X-ray diffraction analysis, molecular modeling, and circular dichroism (CD) spectroscopy. Difunctional 3,7-dibenzylidenebicyclo[3.3.1]nonanes, such as and , exhibited intense CD couplets, arising from the exciton coupling between the two unsaturated chromophores. The observed negative sign of the exciton couplets is congruent with the negative twist (negative... (More)
Synthesis of several enantiomerically pure unsaturated bicyclo[3.3.1]nonane and related brexane (tricyclo[4.3.0.0(3,7) ]nonane) derivatives bearing exocyclic benzylidene substituents from readily available (+)-(1S,5S)-bicyclo[3.3.1]nonane-2,6-dione was accomplished. Molecular geometry and chiroptical properties of compounds with enone and styrene chromophores were studied by X-ray diffraction analysis, molecular modeling, and circular dichroism (CD) spectroscopy. Difunctional 3,7-dibenzylidenebicyclo[3.3.1]nonanes, such as and , exhibited intense CD couplets, arising from the exciton coupling between the two unsaturated chromophores. The observed negative sign of the exciton couplets is congruent with the negative twist (negative chirality) defined by the two interacting transition dipoles. The sign of the Cotton effect corresponding to the π→π* transitions in the CD spectra of monoenone and tricyclic brexane acetate was correlated with the intrinsic dissymmetry (helicity) of the styrene chromophore. Chirality 27:728-737, 2015. © 2015 Wiley Periodicals, Inc. (Less)
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; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chirality
volume
27
issue
10
pages
728 - 737
publisher
John Wiley & Sons Inc.
external identifiers
  • pmid:26415852
  • wos:000362160700009
  • scopus:84942819016
  • pmid:26415852
ISSN
1520-636X
DOI
10.1002/chir.22480
language
English
LU publication?
yes
id
a4b75f9f-39f2-4875-81fa-b39e8ef569b2 (old id 8034611)
date added to LUP
2016-04-01 09:59:43
date last changed
2022-01-25 18:43:44
@article{a4b75f9f-39f2-4875-81fa-b39e8ef569b2,
  abstract     = {{Synthesis of several enantiomerically pure unsaturated bicyclo[3.3.1]nonane and related brexane (tricyclo[4.3.0.0(3,7) ]nonane) derivatives bearing exocyclic benzylidene substituents from readily available (+)-(1S,5S)-bicyclo[3.3.1]nonane-2,6-dione was accomplished. Molecular geometry and chiroptical properties of compounds with enone and styrene chromophores were studied by X-ray diffraction analysis, molecular modeling, and circular dichroism (CD) spectroscopy. Difunctional 3,7-dibenzylidenebicyclo[3.3.1]nonanes, such as and , exhibited intense CD couplets, arising from the exciton coupling between the two unsaturated chromophores. The observed negative sign of the exciton couplets is congruent with the negative twist (negative chirality) defined by the two interacting transition dipoles. The sign of the Cotton effect corresponding to the π→π* transitions in the CD spectra of monoenone and tricyclic brexane acetate was correlated with the intrinsic dissymmetry (helicity) of the styrene chromophore. Chirality 27:728-737, 2015. © 2015 Wiley Periodicals, Inc.}},
  author       = {{Stončius, Sigitas and Neniškis, Algirdas and Loganathan, Nagarajan and Wendt, Ola}},
  issn         = {{1520-636X}},
  language     = {{eng}},
  number       = {{10}},
  pages        = {{728--737}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{Chirality}},
  title        = {{Synthesis, Molecular Structure, and Chiroptical Properties of Dibenzylidene Derivatives of Bicyclo[3.3.1]nonane and Brexane.}},
  url          = {{http://dx.doi.org/10.1002/chir.22480}},
  doi          = {{10.1002/chir.22480}},
  volume       = {{27}},
  year         = {{2015}},
}