2019
DOI: 10.1021/acs.orglett.9b03866
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Redefining the Impact of Boltzmann Analysis in the Stereochemical Assignment of Polar and Flexible Molecules by NMR Calculations

Abstract: The in silico assignment of polyhydroxylated compounds represents a major challenge given the thus far unsolved problem of inappropriate description of the conformational amplitudes. Herein, we report a conceptually novel stochastic approach based on the creation and evaluation of random artificial ensembles, which could provide a new paradigm for computing NMR properties of flexible molecules. The strategy was successfully tested under the DP4/DP4+ platforms using a large set of compounds belonging to the hya… Show more

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Cited by 50 publications
(76 citation statements)
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“…Additionally, the y‐intercepts deviated ~0.006 ppm for the 1 H scaling factors and by <0.3 ppm for the 13 C scaling factors (Tables and ). Thus, while including conformationally flexible compounds in the test set increases the deviation of the chemical shifts, the error is within the expected error bars for experimental chemical shifts and scaling factors changed to only a small degree, suggesting that using rigid test sets when determining scaling factors is not problematic, consistent with the general view that problems with computed shifts for flexible molecules likely result from issues with capturing all relevant conformers and computing accurate relative free energies rather than problems with predicting shifts for a given geometry …”
Section: Resultssupporting
confidence: 63%
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“…Additionally, the y‐intercepts deviated ~0.006 ppm for the 1 H scaling factors and by <0.3 ppm for the 13 C scaling factors (Tables and ). Thus, while including conformationally flexible compounds in the test set increases the deviation of the chemical shifts, the error is within the expected error bars for experimental chemical shifts and scaling factors changed to only a small degree, suggesting that using rigid test sets when determining scaling factors is not problematic, consistent with the general view that problems with computed shifts for flexible molecules likely result from issues with capturing all relevant conformers and computing accurate relative free energies rather than problems with predicting shifts for a given geometry …”
Section: Resultssupporting
confidence: 63%
“…With the inclusion of conformationally flexible compounds, root‐mean‐square deviations for the 1 H and 13 C chemical shifts increased by 0.0053 and 0.0831 ppm, respectively, for the gas optimized chloroform scaling factors (Table ), relative to previously reported shifts using a test set composed of small, rigid molecules . Similar differences were observed for molecules optimized with implicit chloroform (Table ).…”
Section: Resultssupporting
confidence: 58%
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“…In addition, ass tructure elucidation continues to head more towardsablack box scenario( e.g.,a pplyingA Il earningt o CASE), [13] identification of complex chemical structures, that test the performance of modern in silico methods will become more important for CASE evolution. [29]…”
Section: Resultsmentioning
confidence: 99%