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Assignment of the absolute configuration of [n]-ladderanes by TD-DFT optical rotation calculations.

Publication ,  Journal Article
Zuber, G; Goldsmith, M-R; Beratan, DN; Wipf, P
Published in: Chirality
October 2005

In this study, we report theoretical specific rotation values for a series of cis-/trans-alkylated-[5]-ladderanes and cis-/trans-methylated-[n]-ladderanes. Using time-dependent density functional response theory optical rotation calculations, we can assign (+) and (-) optical rotation signs to trans-(S)-alkyl-[5]-ladderane and trans-(R)-alkyl-[5]-ladderane configurations, respectively. In order to qualitatively validate our absolute configuration predictions, we computed optical rotation values at three different levels of theory--B3LYP, RI-BP86, and Hartree-Fock--using the aug-cc-pVDZ basis set. We observe a novel rung-parity-controlled oscillatory optical rotatory phenomenon in our computations, which, to the best of our knowledge, has never been reported or observed before. Furthermore, this preliminary analysis of optical rotation properties in this class of compounds should facilitate the correct absolute stereochemical assignment of natural and synthetic ladderanes, such as the trans-isomer of pentacyclic C(20)-fatty acid methyl ester (pentacycloanammoxic methyl ester), without the need for derivatization, in particular for cases where NMR or X-ray crystal structures are not readily available.

Duke Scholars

Published In

Chirality

DOI

EISSN

1520-636X

ISSN

0899-0042

Publication Date

October 2005

Volume

17

Issue

8

Start / End Page

507 / 510

Related Subject Headings

  • Organic Chemistry
  • Optical Rotation
  • Molecular Structure
  • Models, Chemical
  • Membrane Lipids
  • Mathematics
  • 3405 Organic chemistry
  • 3404 Medicinal and biomolecular chemistry
  • 3401 Analytical chemistry
  • 0306 Physical Chemistry (incl. Structural)
 

Citation

APA
Chicago
ICMJE
MLA
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Zuber, G., Goldsmith, M.-R., Beratan, D. N., & Wipf, P. (2005). Assignment of the absolute configuration of [n]-ladderanes by TD-DFT optical rotation calculations. Chirality, 17(8), 507–510. https://doi.org/10.1002/chir.20190
Zuber, Gérard, Michael-Rock Goldsmith, David N. Beratan, and Peter Wipf. “Assignment of the absolute configuration of [n]-ladderanes by TD-DFT optical rotation calculations.Chirality 17, no. 8 (October 2005): 507–10. https://doi.org/10.1002/chir.20190.
Zuber G, Goldsmith M-R, Beratan DN, Wipf P. Assignment of the absolute configuration of [n]-ladderanes by TD-DFT optical rotation calculations. Chirality. 2005 Oct;17(8):507–10.
Zuber, Gérard, et al. “Assignment of the absolute configuration of [n]-ladderanes by TD-DFT optical rotation calculations.Chirality, vol. 17, no. 8, Oct. 2005, pp. 507–10. Epmc, doi:10.1002/chir.20190.
Zuber G, Goldsmith M-R, Beratan DN, Wipf P. Assignment of the absolute configuration of [n]-ladderanes by TD-DFT optical rotation calculations. Chirality. 2005 Oct;17(8):507–510.
Journal cover image

Published In

Chirality

DOI

EISSN

1520-636X

ISSN

0899-0042

Publication Date

October 2005

Volume

17

Issue

8

Start / End Page

507 / 510

Related Subject Headings

  • Organic Chemistry
  • Optical Rotation
  • Molecular Structure
  • Models, Chemical
  • Membrane Lipids
  • Mathematics
  • 3405 Organic chemistry
  • 3404 Medicinal and biomolecular chemistry
  • 3401 Analytical chemistry
  • 0306 Physical Chemistry (incl. Structural)