Cart
Article
Assigning the Stereochemistry of Pairs of Diastereoisomers Using GIAO NMR Shift Calculation
Full Text HTML
Hi-Res PDFPurchase the full-text
- PDF/HTML,
figures/images,
references and tables,
(where available)
Section:Abstract
GIAO NMR chemical shifts have been calculated for a set of 28 pairs of diastereoisomers in order to test the ability of NMR shift calculation to distinguish between diastereomeric structures. We compare the performance of several different parameters for quantifying the agreement between calculated and experimental shifts from the point of view of assigning structures and introduce a new parameter, CP3, based on comparing differences in calculated shift with differences in experimental shift, which is significantly more successful at making correct structure assignments with high confidence than are the currently used parameters of the mean absolute error and the correlation coefficient. Using our new parameter in conjunction with Bayes’ theorem, stereostructure assignments can be made with quantifiable confidence using shifts obtained in single point calculations on molecular mechanics geometries without computationally expensive ab initio geometry optimization.
Citing Articles
Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.
This article has been cited by 8 ACS Journal articles (5 most recent appear below).
Computational Prediction of 1H and 13C Chemical Shifts: A Useful Tool for Natural Product, Mechanistic, and Synthetic Organic Chemistry
Michael W. Lodewyk, Matthew R. Siebert, and Dean J. TantilloChemical Reviews2011 Article ASAPComputational Prediction of 1H and 13C Chemical Shifts: A Useful Tool for Natural Product, Mechanistic, and Synthetic Organic Chemistry
Michael W. Lodewyk, Matthew R. Siebert, and Dean J. TantilloChemical Reviews2011 Article ASAP
Regression Formulas for Density Functional Theory Calculated 1H and 13C NMR Chemical Shifts in Toluene-d8
Ivan A. Konstantinov and Linda J. BroadbeltThe Journal of Physical Chemistry A2011 115 (44), 12364-12372Regression Formulas for Density Functional Theory Calculated 1H and 13C NMR Chemical Shifts in Toluene-d8
Ivan A. Konstantinov and Linda J. BroadbeltThe Journal of Physical Chemistry A2011 115 (44), 12364-12372This study aimed at investigating the performance of a series of basis sets, density functional theory (DFT) functionals, and the IEF-PCM solvation model in the accurate calculation of 1H and 13C NMR chemical shifts in toluene-d8. We demonstrated that, on ...
Vicinal 1H–1H NMR Coupling Constants from Density Functional Theory as Reliable Tools for Stereochemical Analysis of Highly Flexible Multichiral Center Molecules
Fabian López-Vallejo, Mabel Fragoso-Serrano, Gloria Alejandra Suárez-Ortiz, Adriana C. Hernández-Rojas, Carlos M. Cerda-García-Rojas, and Rogelio Pereda-MirandaThe Journal of Organic Chemistry2011 76 (15), 6057-6066Vicinal 1H–1H NMR Coupling Constants from Density Functional Theory as Reliable Tools for Stereochemical Analysis of Highly Flexible Multichiral Center Molecules
Fabian López-Vallejo, Mabel Fragoso-Serrano, Gloria Alejandra Suárez-Ortiz, Adriana C. Hernández-Rojas, Carlos M. Cerda-García-Rojas, and Rogelio Pereda-MirandaThe Journal of Organic Chemistry2011 76 (15), 6057-6066A protocol for stereochemical analysis, based on the systematic comparison between theoretical and experimental vicinal 1H–1H NMR coupling constants, was developed and applied to a series of flexible compounds (1–8) derived from the 6-heptenyl-5,6-dihydro-...
1H NMR Chemical Shift Calculations as a Probe of Supramolecular Host–Guest Geometry
Jeffrey S. Mugridge, Robert G. Bergman, and Kenneth N. RaymondJournal of the American Chemical Society2011 133 (29), 11205-112121H NMR Chemical Shift Calculations as a Probe of Supramolecular Host–Guest Geometry
Jeffrey S. Mugridge, Robert G. Bergman, and Kenneth N. RaymondJournal of the American Chemical Society2011 133 (29), 11205-11212The self-assembled supramolecular host [Ga4L6]12- (1; L = 1,5-bis[2,3-dihydroxybenzamido]naphthalene) can encapsulate cationic guest molecules within its hydrophobic cavity and catalyze the chemical transformations of bound guests. The cavity of host 1 is ...
Addressing the Stereochemistry of Complex Organic Molecules by Density Functional Theory-NMR: Vannusal B in Retrospective
Giacomo Saielli, K. C. Nicolaou, Adrian Ortiz, Hongjun Zhang, and Alessandro BagnoJournal of the American Chemical Society2011 133 (15), 6072-6077Addressing the Stereochemistry of Complex Organic Molecules by Density Functional Theory-NMR: Vannusal B in Retrospective
Giacomo Saielli, K. C. Nicolaou, Adrian Ortiz, Hongjun Zhang, and Alessandro BagnoJournal of the American Chemical Society2011 133 (15), 6072-6077We have employed density functional theory (DFT) protocols to calculate the NMR properties of the vannusals, a class of natural products whose structures have been the subject of recent investigations. The originally assigned structure of vannusal B was ...
Tools
-
Add to Favorites
-
Download Citation
-
Email a Colleague -
Permalink
Order Reprints
Rights & Permissions
Citation Alerts
History
- Published In Issue June 19, 2009
- Article ASAPMay 21, 2009
- Received: February 24, 2009
ACS
Network
Facebook
Tweet This
CiteULike
Newsvine
Digg This
Delicious
