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. 2011 Jun 9;115(22):5665-73.
doi: 10.1021/jp202501y. Epub 2011 May 13.

A single chiroptical spectroscopic method may not be able to establish the absolute configurations of diastereomers: dimethylesters of hibiscus and garcinia acids

Prasad L Polavarapu  1 , Emily A Donahue, Ganesh Shanmugam, Giovanni Scalmani, Edward K Hawkins, Carmelo Rizzo, Ibrahim Ibnusaud, Grace Thomas, Deenamma Habel, Dellamol Sebastian
Affiliations

A single chiroptical spectroscopic method may not be able to establish the absolute configurations of diastereomers: dimethylesters of hibiscus and garcinia acids

Prasad L Polavarapu et al. J Phys Chem A. .

Abstract

Electronic circular dichroism (ECD), optical rotatory dispersion (ORD), and vibrational circular dichroism (VCD) spectra of hibiscus acid dimethyl ester have been measured and analyzed in combination with quantum chemical calculations of corresponding spectra. These results, along with those reported previously for garcinia acid dimethyl ester, reveal that none of these three (ECD, ORD, or VCD) spectroscopic methods, in isolation, can unequivocally establish the absolute configurations of diastereomers. This deficiency is eliminated when a combined spectral analysis of either ECD and VCD or ORD and VCD methods is used. It is also found that the ambiguities in the assignment of absolute configurations of diastereomers may also be overcome when unpolarized vibrational absorption is included in the spectral analysis.

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Figures

Figure 1
Figure 1
Experimental EA (bottom) and ECD (top) spectra for dimethylesters of hibiscus acid (HADE) and garcinia acid (GADE) in CH3CN and population-weighted corresponding spectra obtained at the CAM-B3LYP/aug-cc-pVDZ-PCM level for (2S,3R)-3 and (2S,3S)-3 diastereomers.
Figure 2
Figure 2
Experimental ORD spectra for (+)-HADE and (+)-GADE in CH3CN and population-weighted ORD spectra obtained at the CAM-B3LYP/aug-cc-pVDZ-PCM level for (2S,3R)-3 and (2S,3S)-3 diastereomers.
Figure 3
Figure 3
Experimental VA (bottom panel) VCD (top panel) spectra for (+)-HADE and (+)-GADE in CH2Cl2.
Figure 4
Figure 4
Comparison of experimental VA (bottom panel) and VCD (top panel) spectra for (+)-HADE in CH2Cl2 with predicted population-weighted spectra at the B3LYP/aug-cc-pVDZ-PCM level for (2S,3R)-3.
Figure 5
Figure 5
Comparison of experimental VA (bottom panel) and VCD (top panel) spectra for (+)-HADE and (+)-GADE in CH2Cl2 with predicted population-weighted spectra for all four diastereomers ((2S,3R)-3, (2S,3S)-3, (2R,3S)-3, and (2R,3R)-3) at the B3LYP/aug-cc-pVDZ-PCM level.
Chart 1
Chart 1
Stereoisomers of 2-Hydroxycitric Acid, Corresponding Lactones and Their Dimethyl Esters
See this image and copyright information in PMC

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References

    1. Ibnusaud I, Thomas PT, Rani RN, Sasi PV, Beena T, Hisham A. Tetrahedron. 2002;58:4887–4892.
    1. Lewis YS, Neelakantan S, Anjanamurthy Curr Sci. 1964;3:82–83.
    2. Lewis YS, Neelakantan S. Phytochemistry. 1965;4:619–625.
    1. Jena BS, Jayaprakasha GK, Singh RP, Sakariah KK. J Agric Food Chem. 2002;50:10–22. - PubMed
    1. Boll PM, Sorensen E, Balieu E. Acta Chem Scand. 1969;23:286–293.
    2. Glusker JP, Minkin JA, Soule FB. Acta Crystallogr. 1972;B28:2499–2505.
    1. Autschbach J. Chirality. 2009;21:E116–E152. - PubMed

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