eprintid: 23372
rev_number: 13
userid: 1419
dir: disk0/00/02/33/72
datestamp: 2014-10-21 17:01:42
lastmod: 2017-10-13 21:56:48
status_changed: 2014-10-21 17:01:42
type: article
metadata_visibility: show
item_issues_count: 0
eprint_status: archive
creators_name: Kondru, RK
creators_name: Lim, S
creators_name: Wipf, P
creators_name: Beratan, DN
creators_email: 
creators_email: 
creators_email: pwipf@pitt.edu
creators_email: 
creators_id: 
creators_id: 
creators_id: PWIPF
creators_id: 
title: Synthetic and model computational studies of molar rotation additivity for interacting chiral centers: a reinvestigation of van't Hoff's principle.
ispublished: pub
divisions: sch_as_chemistry
full_text_status: public
keywords: Chemistry, Physical, Models, Chemical, Oxazoles, Reproducibility of Results, Stereoisomerism
abstract: When plane-polarized light impinges on a solution of optically active molecules, the polarization of the light that emerges is rotated. This simple phenomenon arises from the interaction of light with matter and is well understood, in principle, van't Hoff's rule of optical superposition correlates the molar rotation with the individual contributions to optical activity of isolated centers of asymmetry. This straightforward empirical additivity rule is rarely used for structure elucidation nowadays because of its limitations in the assessment of conformationally restricted or interacting chiral centers. However, additivity can be used successfully to assign the configuration of complex natural products such as hennoxazole A if appropriate synthetic partial structures are available. Therefore, van't Hoff's principle is a powerful stereochemical complement to natural products' total synthesis. The quest for reliable quantitative methods to calculate the angle of rotation a priori has been underway for a long time. Both classical and quantum methods for calculating molar rotation have been developed. Of particular practical importance for determining the absolute structure of molecules by calculation is the manner in which interactions between multiple chiral centers in a single molecule are included, leading to additive or non-additive optical rotation angles. This problem is addressed here using semi-empirical electronic structure models and the Rosenfeld equation.
date: 1997
date_type: published
publication: Chirality
volume: 9
number: 5-6
pagerange: 469 - 477
event_location: United States
refereed: TRUE
issn: 0899-0042
funders: NIAID NIH HHS (AI/GM34914)
id_number: 10.1002/(SICI)1520-636X(1997)9:5/6<469::AID-CHIR13>3.0.CO;2-M
other_id: 10.1002/(SICI)1520-636X(1997)9:5/6<469::AID-CHIR13>3.0.CO;2-M
pmid: 9329177
mesh_headings: Chemistry, Physical--methods
mesh_headings: Models, Chemical
mesh_headings: Oxazoles--chemistry
mesh_headings: Reproducibility of Results
mesh_headings: Stereoisomerism
chemical_names: Oxazoles
chemical_names: hennoxazole A
language: eng
citation:   Kondru, RK and Lim, S and Wipf, P and Beratan, DN  (1997) Synthetic and model computational studies of molar rotation additivity for interacting chiral centers: a reinvestigation of van't Hoff's principle.  Chirality, 9 (5-6).  469 - 477.  ISSN 0899-0042     
document_url: http://d-scholarship-dev.library.pitt.edu/23372/1/licence.txt