eprintid: 19979
rev_number: 22
userid: 1419
dir: disk0/00/01/99/79
datestamp: 2013-11-12 17:17:12
lastmod: 2021-06-12 22:55:54
status_changed: 2013-11-12 17:17:12
type: article
metadata_visibility: show
item_issues_count: 0
eprint_status: archive
creators_name: Zuber, G
creators_name: Goldsmith, MR
creators_name: Beratan, DN
creators_name: Wipf, P
creators_email: 
creators_email: 
creators_email: 
creators_email: pwipf@pitt.edu
creators_id: 
creators_id: 
creators_id: 
creators_id: PWIPF
title: Assignment of the absolute configuration of [n]-ladderanes by TD-DFT optical rotation calculations
ispublished: pub
divisions: sch_as_chemistry
full_text_status: public
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 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.
date: 2005-10-10
date_type: published
publication: Chirality
volume: 17
number: 8
pagerange: 507 - 510
refereed: TRUE
issn: 0899-0042
id_number: 10.1002/chir.20190
pmid: 16121333
mesh_headings: Mathematics
mesh_headings: Membrane Lipids--chemistry
mesh_headings: Models, Chemical
mesh_headings: Molecular Structure
mesh_headings: Optical Rotation
chemical_names: Membrane Lipids
citation:   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     
document_url: http://d-scholarship-dev.library.pitt.edu/19979/1/licence.txt