Regular Article

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

  1. Gérard Zuber1,
  2. Michael-Rock Goldsmith1,
  3. David N. Beratan1,*,
  4. Peter Wipf2,*

Article first published online: 24 AUG 2005

DOI: 10.1002/chir.20190

Issue

Chirality

Chirality

Volume 17, Issue 8, pages 507–510, 2005

Additional Information

How to Cite

Zuber, G., Goldsmith, M.-R., Beratan, D. N. and Wipf, P. (2005), Assignment of the absolute configuration of [n]-ladderanes by TD-DFT optical rotation calculations. Chirality, 17: 507–510. doi: 10.1002/chir.20190

Author Information

  1. 1

    Department of Chemistry, Duke University, Durham, North Carolina 27708

  2. 2

    Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260

*Department of Chemistry, Duke University, Durham, NC 27708

  1. †

    This article includes Supplementary Material available via the Internet at http://www.interscience.wiley.com/jpages/0899-0042/suppmat

Publication History

  1. Issue published online: 30 AUG 2005
  2. Article first published online: 24 AUG 2005
  3. Manuscript Accepted: 25 APR 2005
  4. Manuscript Received: 23 MAR 2005

Funded by

  • Swiss National Science Foundation
  • National Institutes of Health/National Institute of General Medical Sciences. Grant Number: NIH/NIGMS 5T32-GM08487
  • Duke University Program in Structural Biology and Biophysics

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Keywords:

  • optical rotation;
  • DFT calculations;
  • absolute configuration;
  • ladderanes

Abstract

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 C20-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. © 2005 Wiley-Liss, Inc. Chirality 17:507–510, 2005.

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