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On the proof and disproof of natural product stereostructures: Characterization and analysis of a twenty-eight member stereoisomer library of murisolins and their Mosher ester derivatives

Curran, DP and Zhang, Q and Lu, H and Gudipati, V (2006) On the proof and disproof of natural product stereostructures: Characterization and analysis of a twenty-eight member stereoisomer library of murisolins and their Mosher ester derivatives. Journal of the American Chemical Society, 128 (30). 9943 - 9956. ISSN 0002-7863

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Abstract

Characterizing a stereoisomer library of 28 of the 64 possible isomers of the acetogenin murisolin, including 24 of the 32 possible diastereomers, provides a complete picture of the spectra of this class of molecules. Remarkably, each of the 32 diastereomers exhibits one of only six sets of substantially identical 1H NMR spectra under standard conditions. These spectra follow directly from a local symmetry analysis of the dihydroxy-THF fragment of the molecule and provide no information about the configuration about the hydroxybutenolide. Eighteen tris-Mosher ester derivatives of library members have been made, and their spectra were analyzed to give a complete picture of the usefulness of chiral derivatives. The tris-Mosher esters of the 64 isomers of murisolin will exhibit 40 sets of spectra: 16 isomers have unique spectra whereas 24 isomers share an identical spectrum with one other isomer. This identity occurs even though the pairs of compounds were already diastereomers (not enantiomers) before the derivatization. The complete set of spectra allows any murisolin or closely related compound to be narrowed to one or two structures by simple matching and without recourse to assignment and subtraction of resonances. The structure of murisolin was proved to be the 4R, 15R, 16R, 19R, 20R, 34S isomer, whereas the assignment of 16,19-cis-murisolin as RRRSSS was changed to the RSSRRS diastereomer and murisolin A is suggested to be RSRRRS. © 2006 American Chemical Society.


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Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Curran, DPcurran@pitt.eduCURRAN
Zhang, Q
Lu, H
Gudipati, V
Date: 2 August 2006
Date Type: Publication
Journal or Publication Title: Journal of the American Chemical Society
Volume: 128
Number: 30
Page Range: 9943 - 9956
DOI or Unique Handle: 10.1021/ja062469l
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0002-7863
MeSH Headings: Acetogenins; Biological Agents--chemistry; Combinatorial Chemistry Techniques; Esters; Fatty Alcohols--chemistry; Furans--chemistry; Lactones--chemistry; Molecular Conformation; Molecular Structure
PubMed ID: 16866554
Date Deposited: 28 May 2013 15:39
Last Modified: 02 Feb 2019 15:59
URI: http://d-scholarship.pitt.edu/id/eprint/18776

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