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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Published in | Journal of organic chemistry Vol. 83; no. 9; pp. 5035 - 5043 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
United States
04.05.2018
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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. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1520-6904 |
DOI: | 10.1021/acs.joc.8b00338 |