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

Zuber, G and Goldsmith, MR and Beratan, DN and Wipf, P (2005) Assignment of the absolute configuration of [n]-ladderanes by TD-DFT optical rotation calculations. Chirality, 17 (8). 507 - 510. ISSN 0899-0042

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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 C2O-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.


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Item Type: Article
Status: Published
CreatorsEmailPitt UsernameORCID
Zuber, G
Goldsmith, MR
Beratan, DN
Wipf, Ppwipf@pitt.eduPWIPF
Date: 10 October 2005
Date Type: Publication
Journal or Publication Title: Chirality
Volume: 17
Number: 8
Page Range: 507 - 510
DOI or Unique Handle: 10.1002/chir.20190
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0899-0042
MeSH Headings: Mathematics; Membrane Lipids--chemistry; Models, Chemical; Molecular Structure; Optical Rotation
PubMed ID: 16121333
Date Deposited: 12 Nov 2013 17:17
Last Modified: 22 Jun 2021 12:55


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