%0 Journal Article
%A Johnson, Jordan
L.
%A Nair, Divya Sadasivan
%A Pillai, Sarath Muraleedharan
%A Johnson, Didimos
%A Kallingathodi, Zabeera
%A Ibnusaud, Ibrahim
%A Polavarapu, Prasad L.
%D 2019
%T Dissymmetry Factor Spectral Analysis Can Provide Useful
Diastereomer Discrimination: Chiral Molecular Structure of an Analogue
of (−)-Crispine A
%U https://acs.figshare.com/articles/journal_contribution/Dissymmetry_Factor_Spectral_Analysis_Can_Provide_Useful_Diastereomer_Discrimination_Chiral_Molecular_Structure_of_an_Analogue_of_-Crispine_A/7938962
%R 10.1021/acsomega.8b03678.s001
%2 https://acs.figshare.com/ndownloader/files/14774066
%K chiral centers
%K crystal X-ray diffraction data
%K chiroptical spectra
%K Dissymmetry Factor Spectral Analysis
%K configuration
%K stereogenic centers
%K Chiral Molecular Structure
%K ECD
%K scheme
%K dissymmetry factor
%K quantum chemical
%K vibrational dissymmetry factor
%K Useful Diastereomer Discrimination
%K EDF
%K ORD
%K diastereomer discrimination tool
%K VDF
%K rotatory dispersion
%K information
%K QC
%K dichroism
%K AC
%K X-ray data
%K VCD
%K chiroptical spectroscopic methods
%X (1R,10bR)-1′-((R)-1,2-Dihydroxyethyl)-1-hydroxy-8,9-dimethoxy1,5,6,10b-tetrahydropyrrolo [2,1-a]isoquinolin-3(2H)-one, an analogue of (−)-crispine A, with three
stereogenic centers is synthesized and its absolute configuration
(AC) established using the combined information derived from the synthetic
scheme and single crystal X-ray diffraction data. The experimental
chiroptical spectra (namely, optical rotatory dispersion (ORD), electronic
circular dichroism (ECD), and vibrational circular dichroism (VCD))
and the corresponding quantum chemical (QC) predicted spectra for
all diastereomers are used to evaluate the AC. The AC of the synthesized
compound could be correctly established using any one of the three
chiroptical spectroscopic methods (ORD, ECD, or VCD) when the relative
configuration is constrained to be that derived from X-ray data or
when the ACs of two of the chiral centers are constrained to be those
derived from the synthetic scheme. In the absence of this outside
information, the QC predicted ORD, ECD, and VCD for incorrect diastereomers
are also found to satisfactorily reproduce the corresponding experimental
spectra. Nevertheless, incorrect diastereomers could be eliminated
when combined electronic dissymmetry factor (EDF) and vibrational
dissymmetry factor (VDF) spectral analyses are included, leaving the
correct diastereomer as the sole choice. Thus, the combined EDF and
VDF spectral analysis is seen to be a helpful diastereomer discrimination
tool.
%I ACS Publications