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The overlooked rotational isomerism of C-glycosyl flavonoids

  • Guohong Zhou
  • Renliang Yan
  • Xiaogen Wang
  • Shaolin Li
  • Jin Lin
  • Jia Liu
  • Zhendong ZhaoEmail author
Article
  • 69 Downloads

Abstract

C-glycosyl flavonoids are important secondary plant metabolites with a wide range of biological activities. Rotational isomerism, arising from restricted bond rotation, has been observed on a portion of C-glycosyl flavonoids. NMR technique contributes most to the observation and research of this phenomenon. Signal duplication in NMR spectra may be the key characteristic of C-glycosyl flavonoids existing as rotamers. Bulky steric hindrance from the substituents at position 7 and sugar moieties are responsible for the restricted bond rotation. There are other influence factors including temperature, solvents, H-bonds and π-stacking, but these are of lesser importance. Difference exists between 8-C-glycosyl flavonoids and their 6-C-glycosyl isomers despite sharing the same flavonoid aglycone and sugar moiety. 8-C-glycosyl flavonoids are more likely to suffer from restricted rotation. The energy barriers between rotamers of C-glycosyl flavonoids seem not high enough for atropisomerism to be realized and the isolation of rotamers should be difficult.

Keywords

Rotational isomerism Rotamer Atropisomerism C-glycosyl flavonoids Restricted rotation 

Abbreviations

HPLC

High performance liquid chromatography

NMR

Nuclear magnetic resonance spectroscopy

Notes

References

  1. Adams R, Yuan HC (1933) The stereochemistry of diphenyls and analogous compounds. Chem Rev 2:261–338CrossRefGoogle Scholar
  2. Adjé FA, Lozano YF, Le Gernevé C et al (2012) Phenolic acid and flavonol water extracts of Delonix regia red flowers. Ind Crops Prod 1:303–310CrossRefGoogle Scholar
  3. Antonio CJ, Delgado G, Salas EM et al (2002) Triterpenes, phenols, and other constituents from the leaves of Ochroma pyramidale (Balsa Wood, Bombacaceae). Preferred Conformations of 8-C-beta-D-glucopyranosyl-apigenin (vitexin). J Mex Chem Soc 3:254–258Google Scholar
  4. Bezuidenhoudt B, Brandt EV, Ferreira D (1987) Flavonoid analogues from Pterocarpus species. Phytochemistry 2:531–535CrossRefGoogle Scholar
  5. Bjoroy O, Rayyan S, Fossen T et al (2009a) Structural properties of anthocyanins: rearrangement of C-glycosyl-3-deoxyanthocyanidins in acidic aqueous solutions. J Agric Food Chem 15:6668–6677CrossRefGoogle Scholar
  6. Bjoroy O, Rayyan S, Fossen T et al (2009b) C-glycosylanthocyanidins synthesized from C-glycosylflavones. Phytochemistry 2:278–287CrossRefGoogle Scholar
  7. Camargo LMDM, Férézou J, Tinoco LW et al (2012) Flavonoids from Mimosa xanthocentra (Leguminosae: Mimosoideae) and molecular modeling studies for isovitexin-2″-O-α-L-rhamnopyranoside rotamers. Phytochem Lett 3:427–431CrossRefGoogle Scholar
  8. Chang CC, Ku AF, Tseng YY et al (2010) 6,8-Di-C-glycosyl flavonoids from Dendrobium huoshanense. J Nat Prod 2:229–232CrossRefGoogle Scholar
  9. Cheng G, Bai Y, Zhao Y et al (2000) Flavonoids from Ziziphus jujuba Mill var. spinosa. Tetrahedron 45:8915–8920CrossRefGoogle Scholar
  10. Courts FL, Williamson G (2015) The occurrence, fate and biological activities of C-glycosyl flavonoids in the human diet. Crit Rev Food Sci Nutr 10:1352–1367CrossRefGoogle Scholar
  11. Davoust D, Massias M, Molho D (1980) 13C NMR investigation of flavonoid C-β-D-glucosides. Detection of a conformational equilibrium. Org Magn Reson 3:218–219CrossRefGoogle Scholar
  12. Díaz JG, de Paz PP, Herz W (2010) New water soluble flavone and xanthone glycosides from Hypericum canariense L. Phytochem Lett 4:171–175CrossRefGoogle Scholar
  13. Eade RA, Hillis WE, Horn D et al (1965) Nuclear magnetic resonance studies. III. Rotational isomerism of some C-glucosylflavonoid acetates. Aust J Chem 5:715–721CrossRefGoogle Scholar
  14. Fan J, Lee I, Lin Y (2015) Flavone glycosides from commercially available Lophatheri Herba and their chromatographic fingerprinting and quantitation. J Food Drug Anal 4:821–827CrossRefGoogle Scholar
  15. Frank JH, Powder-George YL, Ramsewak RS et al (2012) Variable-temperature 1H-NMR studies on two C-glycosylflavones. Molecule 7:7914–7926CrossRefGoogle Scholar
  16. Gentili B, Horowitz R (1968) Flavonoids of citrus. IX. C-Glycosylflavones and a nuclear magnetic resonance method for differentiating 6- and 8-C-glycosyl isomers. J Org Chem 4:1571–1577CrossRefGoogle Scholar
  17. Glunz PW (2018) Recent encounters with atropisomerism in drug discovery. Bioorg Med Chem Lett 28:53–60CrossRefGoogle Scholar
  18. Han QB, Lee SF, Qiao CF et al (2005) Complete NMR assignments of the antibacterial biflavonoid GB1 from Garcinia kola. Chem Pharm Bull 8:1034–1036CrossRefGoogle Scholar
  19. Hatano T, Mizuta S, Ito H et al (1999) C-Glycosidic flavonoids from Cassia occidentalis. Phytochemistry 7:1379–1383CrossRefGoogle Scholar
  20. Hillis WE, Horn D (1965) Nuclear magnetic resonance spectra and structures of some C-glycosyl flavonoids. Aust J Chem 4:531–542CrossRefGoogle Scholar
  21. Kato T, Morita Y (1993) The rotational isomers of peracetylated C-glycosylflavones. Heterocycles 2:965–973Google Scholar
  22. Kumarasamy E, Raghunathan R, Sibi MP et al (2015) Nonbiaryl and heterobiaryl atropisomers: molecular templates with promise for atropselective chemical transformations. Chem Rev 20:11239–11300CrossRefGoogle Scholar
  23. Kumazawa T, Kimura T, Matsuba S et al (2001) Synthesis of 8-C-Glucosylflavones. Carbohydr Res 3:183–193CrossRefGoogle Scholar
  24. LaPlante SR, Edwards PJ, Fader LD et al (2011) Revealing atropisomer axial chirality in drug discovery. ChemMedChem 3:505–513CrossRefGoogle Scholar
  25. Latté KP, Ferreira D, Venkatraman MS et al (2002) O-Galloyl-C-glycosylflavones from Pelargonium reniforme. Phytochemistry 4:419–424CrossRefGoogle Scholar
  26. Lewis K, Maxwell A, McLean S et al (2000) Room-temperature (1H, 13C) and variable-temperature (1H) NMR studies on spinosin. Magn Reson Chem 9:771–774CrossRefGoogle Scholar
  27. Liu XH, Wang F, Liang H et al (2004) Structure identification of jujubosike D. Acta Chim Sin 8:601–604Google Scholar
  28. Markham KR, Mues R, Stoll M et al (1987) NMR-spectra of flavone di-C-glycosides from Apometzgeria pubescens and the detection of rotational-isomerism in 8-C-hexosylflavones. Verlag Zeitschrift für Naturforschung 42:1039–1042CrossRefGoogle Scholar
  29. Mizuno T, Yabuya T, Kitajima J et al (2013) Identification of novel C-glycosylflavones and their contribution to flower colour of the Dutch iris cultivars. Plant Physiol Biochem 72:116–124CrossRefGoogle Scholar
  30. Moss GP (1996) Basic terminology of stereochemistry (IUPAC Recommendations 1996). Pure Appl Chem 12:2193–2222CrossRefGoogle Scholar
  31. Mustafa K, Kjaergaard HG, Perry NB et al (2003) Hydrogen-bonded rotamers of 2′,4′,6′-trihydroxy-3′-formyldihydrochalcone, an intermediate in the synthesis of a dihydrochalcone from Leptospermum recurvum. Tetrahedron 32:6113–6120CrossRefGoogle Scholar
  32. Nassar MI (2006) Flavonoid triglycosides from the seeds of Syzygium aromaticum. Carbohydr Res 1:160CrossRefGoogle Scholar
  33. Nikolov N, Dellamonic G, Chopin J (1981) Di-C-glycosylflavones from Crataegus monogyna. Phytochemistry 12:2780–2781CrossRefGoogle Scholar
  34. Norbaek R, Brandt K, Kondo T (2000) Identification of flavone C-glycosides including a new flavonoid chromophore from barley leaves (Hordeum vulgare L.) by improved NMR techniques. J Agric Food Chem 5:1703–1707CrossRefGoogle Scholar
  35. Osorio E, Londoño J, Bastida J (2013) Low-density lipoprotein (LDL)-antioxidant biflavonoids from Garcinia madruno. Molecules 5:6092–6100CrossRefGoogle Scholar
  36. Pacifico M, Napolitano A, Masullo M et al (2011) Metabolite fingerprint of capim dourado (Syngonanthus nitens), a basis of Brazilian handcrafts. Ind Crops Prod 2:488–496CrossRefGoogle Scholar
  37. Pryakhina NI, Sheichenko V, Blinova KF (1984) Acylated C-glycosides of Iris lactea. Chem Nat Compd 5:554–559CrossRefGoogle Scholar
  38. Rabe C, Steenkamp JA, Joubert E et al (1994) Phenolic metabolites from rooibos tea (Aspalathus Linearis). Phytochemistry 35:1559–1565CrossRefGoogle Scholar
  39. Rayyan S, Fossen T, Andersen OM (2005a) Flavone C-glycosides from leaves of Oxalis triangularis. J Agric Food Chem 26:10057–10060CrossRefGoogle Scholar
  40. Rayyan S, Fossen T, Solheim NH et al (2005b) Isolation and identification of flavonoids, including flavone rotamers, from the herbal drug ‘Crataegi folium cum flore’ (hawthorn). Phytochem Anal 5:334–341CrossRefGoogle Scholar
  41. Rayyan S, Fossen T, Andersen OM (2010) Flavone C-glycosides from seeds of fenugreek, Trigonella foenum-graecum L. J Agric Food Chem 12:7211–7217CrossRefGoogle Scholar
  42. Shananatidi H, Bareli KH (1970) A convenient method for obtaining free energies of activation by the coalescence temperature of an unequal doublet. J Phys Chem 4:961–963CrossRefGoogle Scholar
  43. Smyth JE, Butler NM, Keller PA (2015) A twist of nature–the significance of atropisomers in biological systems. Nat Prod Rep 11:1562–1583CrossRefGoogle Scholar
  44. Suzuki R, Okada Y, Okuyama T (2003) Two flavone C-glycosides from the style of Zea mays with glycation inhibitory activity. J Nat Prod 4:564–565CrossRefGoogle Scholar
  45. Talhi O, Silva AMS (2012) Advances in C-glycosylflavonoid Research. Curr Org Chem 16:859–896CrossRefGoogle Scholar
  46. Tan P, Hou C, Liu Y et al (1991) Swertipunicoside. The first bisxanthone C-glycoside. J Org Chem 25:7130–7133CrossRefGoogle Scholar
  47. Toenjes ST, Gustafson JL (2018) Atropisomerism in medicinal chemistry: challenges and opportunities. Future Med Chem 4:409CrossRefGoogle Scholar
  48. Wang JN, Hou CY, Liu YL et al (1994) Swertifrancheside, an HIV-reverse transcriptase inhibitor and the first flavone-xanthone dimer, from Swertia franchetiana. J Nat Prod 2:211–217CrossRefGoogle Scholar
  49. Wang B, Zhu H, Wang D et al (2013) New spinosin derivatives from the seeds of Ziziphus mauritiana. Nat Prod Bioprospect 3:93–98CrossRefGoogle Scholar
  50. Whaley AK, Ebrahim W, El-Neketi M et al (2017) New acetylated flavone C-glycosides from Iris lactea. Tetrahedron Lett 22:2171–2173CrossRefGoogle Scholar
  51. Xiao J, Capanoglu E, Jassbi AR et al (2016) Advance on the flavonoid C-glycosides and health benefits. Crit Rev Food Sci Nutr 56:29–45CrossRefGoogle Scholar
  52. Xie YY, Xu ZL, Wang H et al (2011) A novel spinosin derivative from Semen Ziziphi Spinosae. J Asian Nat Prod Res 12:1151–1157CrossRefGoogle Scholar
  53. Yamamoto G (1992) Rotational isomerism and atropisomerism in acetal derivatives of 1,2,3,4-Tetrafluorotriptycene-9-carbaldehyde. Chem Soc Jpn 7:1967–1975CrossRefGoogle Scholar
  54. Yang CR, Jin YX, Zhang JZ et al (2010) Studies on chemical constituents from leaves of Dipsacus sativus. Zhongguo Yaoxue Zazhi 8:578–580Google Scholar
  55. Yang D, Xie H, Jia X et al (2015) Flavonoid C-glycosides from star fruit and their antioxidant activity. J Funct Foods 16:204–210CrossRefGoogle Scholar
  56. Ye XL (1999) Stereochemistry. Peking University Press, BeijingGoogle Scholar
  57. Zhang PC, Wang YH, Liu X et al (2002) Conformational study of 8-C-glucosyl-prunetin by dynamic NMR spectroscopy. Chin Chem Lett 7:645–648Google Scholar
  58. Zhang PC, Wang YH, Liu X et al (2003) Conformational study of 8-C-glucosyl-prunetin by dynamic NMR spectroscopy. Acta Chim Sin 7:1157–1160Google Scholar
  59. Zhou G, Tang L, Wang T et al (2016) Phytochemistry and pharmacological activities of Vaccaria hispanica (Miller) Rauschert: a review. Phytochem Rev 5:813–827CrossRefGoogle Scholar
  60. Zhou G, Wu H, Wang T et al (2017) C-glycosylflavone with rotational isomers from Vaccaria hispanica (Miller) Rauschert seeds. Phytochem Lett 19:241–247CrossRefGoogle Scholar
  61. Zuo YM, Liu DH, Zhang ZL et al (2014) Study on chemical components of Tripterospermum chinense. Zhongyaocai 11:2002–2004Google Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  • Guohong Zhou
    • 1
  • Renliang Yan
    • 1
  • Xiaogen Wang
    • 1
  • Shaolin Li
    • 1
  • Jin Lin
    • 1
  • Jia Liu
    • 1
  • Zhendong Zhao
    • 1
    Email author
  1. 1.Guangdong Food and Drug Vocational CollegeGuangzhouChina

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