D iCE: Diastereomeric in Silico Chiral Elucidation, Expanded DP4 Probability Theory Method for Diastereomer and Structural Assignment

NMR chemical shift prediction at the B3LYP/cc-pVDZ level of theory was used to develop a highly accurate probability theory algorithm for the determination of the stereochemistry of diastereomers as well as the regiochemistry. DFT-GIAO calculations were performed for each conformer using geometry op...

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Bibliographic Details
Published in:Journal of organic chemistry 2018-05, Vol.83 (9), p.5035-5043
Main Authors: Xin, Dongyue, Jones, Paul-James, Gonnella, Nina C
Format: Article
Language:English
Online Access:Get full text
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Summary:NMR chemical shift prediction at the B3LYP/cc-pVDZ level of theory was used to develop a highly accurate probability theory algorithm for the determination of the stereochemistry of diastereomers as well as the regiochemistry. DFT-GIAO calculations were performed for each conformer using geometry optimization and a CPCM solvent model. Boltzmann averaged shielding constants were converted to chemical shifts for H and C, using the generalized linear scaling terms determined in four different solvents for H and C and extended to N in DMSO. The probability theory algorithm, D iCE, was based on the DP4 method and developed for H, C, and N NMR using individual and combined probability data. The chemical shift calculation errors were fitted to a Student's t-distribution for H and C and a normal distribution for N. The application yielded a high accuracy for structural assignment with a low computational cost.
ISSN:1520-6904
DOI:10.1021/acs.joc.8b00338