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Synthetic and model computational studies of molar rotation additivity for interacting chiral centers: a reinvestigation of van't Hoff's principle.

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

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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.


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Item Type: Article
Status: Published
CreatorsEmailPitt UsernameORCID
Kondru, RK
Lim, S
Wipf, Ppwipf@pitt.eduPWIPF
Beratan, DN
Date: 1997
Date Type: Publication
Journal or Publication Title: Chirality
Volume: 9
Number: 5-6
Page Range: 469 - 477
DOI or Unique Handle: 10.1002/(sici)1520-636x(1997)9:5/6<469::aid-chir13>;2-m
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
Uncontrolled Keywords: Chemistry, Physical, Models, Chemical, Oxazoles, Reproducibility of Results, Stereoisomerism
ISSN: 0899-0042
Funders: NIAID NIH HHS (AI/GM34914)
MeSH Headings: Chemistry, Physical--methods; Models, Chemical; Oxazoles--chemistry; Reproducibility of Results; Stereoisomerism
Other ID: 10.1002/(SICI)1520-636X(1997)9:5/6<469::AID-CHIR13>3.0.CO;2-M
PubMed ID: 9329177
Date Deposited: 21 Oct 2014 17:01
Last Modified: 13 Oct 2017 21:56


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