Advertisement

Journal of Natural Medicines

, Volume 73, Issue 1, pp 236–243 | Cite as

Preparation of menisdaurigenin and related compounds

  • Rie Shirakawa
  • Sanami Ishikawa
  • Mizuki Takahasi
  • Yuuka Ueno
  • Yoshinori Uekusa
  • Yuji Narukawa
  • Takeshi Sugai
  • Fumiyuki KiuchiEmail author
Note
  • 88 Downloads

Abstract

Menisdaurin (1), a cyano glucoside, was first isolated in 1978 from Menispermum dauricum (Menispermaceae) and named after the plant. It has been also isolated from several plant sources. The stereochemistry of the aglycone part was first reported as (Z,4R,6S)-enantiomer of (4,6-dihydroxy-2-cyclohexen-1-ylidene)acetonitrile based on the CD spectrum of menisdaurilide (2), the α,β-unsaturated γ-lactone obtained by an acid hydrolysis of menisdaurin. Later, the absolute stereochemistry was revised as (Z,4S,6R) by X-ray crystal analysis of 1 isolated from Saniculiphyllum guangxiens. The aglycone part of menisdaurin (1) has not been obtained from 1, because an acid hydrolysis of 1 gave menisdaurilide (2), and enzymatic hydrolysis with emulsin did not give the aglycone. On the other hand, a compound named coculauril (3) was isolated from Cocculus lauriforius. This compound has the same planner structure corresponding to the aglycone of 1, but the stereochemistry was reported to be (E,4R,6S). Here, we confirmed the absolute stereochemistry of 1 by Mosher’s method to be (Z,4S,6R), and prepared the aglycone of 1, i.e., menisdaurigenin (4) by an enzymatic hydrolysis of 1. We also revealed that 4 is a different compound from 3 and unstable in water and MeOH.

Keywords

Sinomenium acutum Menisdaurin Menisdaurigenin Enzymatic hydrolysis Color change 

Notes

Acknowledgements

The authors are grateful to Dr. Tomoko Sano of Tsumura & Co. for providing information and materials of Sinomenium root. This work was supported in part by the MEXT-Supported Program for the Strategic Research Foundation at Private Universities (S1101003) from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

References

  1. 1.
    Takahashi K, Matsuzawa S, Takani M (1978) Studies on the constituents of medicinal plants. XX. The constituent of the vines of Menisperum dauricum. Chem Pharm Bull 26:1677–1681CrossRefGoogle Scholar
  2. 2.
    Ueda K, Yasutomi K, Mori I (1983) Structure of a new cyanoglucoside from Ilex warburgii LOESN. Chem Lett 1983:149–150CrossRefGoogle Scholar
  3. 3.
    Nahrstedt A, Wray V (1990) Structural revision of a putative cyanogenic glucoside from Ilex aquifolium. Phytochemistry 29:3934–3936CrossRefGoogle Scholar
  4. 4.
    Otsuka H, Ito A, Kawamata K, Kasai R, Yamasaki K, Satoh T (1993) Butenolides from Sinomenium acutum. Phytochemistry 33:389–392CrossRefGoogle Scholar
  5. 5.
    Nakanishi T, Nishi M, Somekawa M, Murata H, Mizuno M, Iinuma M, Tanaka T, Murata J, Lang FA, Inada A (1994) Structures of new and known cyanoglucosides from a north American plant, Purshia tridentata DC. Chem Pharm Bull 42:2251–2255CrossRefGoogle Scholar
  6. 6.
    Athikomkulchai S, Ruangrungsi N, Sekine T, Sugino M, Igarashi K, Ikegami F (2003) Chemical constituents of Bauhinia sirindhorniae. Nat Med 57:150–153Google Scholar
  7. 7.
    Seigler DS, Pauli GF, Fröhlich R, Wegelius E, Nahrstedt A, Glander KE, Ebinger JE (2005) Cyanogenic glycosides and menisdaurin from Guazuma ulmifolia, Ostrya virginiana, Tiquilia plicata, and Tiquilia canescens. Phytochemistry 66:1567–1580CrossRefGoogle Scholar
  8. 8.
    Niu F, Cui Z, Chang HT, Jiang Y, Chen FK, Tu PF (2006) Constituents from the roots of Semiaquilegia adoxoides. Chin J Chem 24:1788–1791CrossRefGoogle Scholar
  9. 9.
    Bikobo DSN, Nkot JL, Mosset P, Atchade AT, Ndongo JT, Pemha R, Pegnyemb DE (2011) Acylsteryl glycosides and other constituents from Campylospermum densiflorum (Ochnaceae). Rasayan J Chem 4:753–763Google Scholar
  10. 10.
    Geng C-A, Huang X-Y, Lei L-G, Zhang X-M, Chen J-J (2012) Chemical constituents of Saniculiphyllum guangxiense. Chem Biodivers 9:1508–1516CrossRefGoogle Scholar
  11. 11.
    Yi X-X, Deng J-G, Gao C-H, Hou X-T, Li F, Wang Z-P, Hao E-W, Xie Y, Du Z-C, Huang H-X, Huang R-M (2015) Four new cyclohexylideneacetonitrile derivatives from the hypocotyl of Mangrove (Bruguiera gymnorrhiza). Molecules 20:14565–14575CrossRefGoogle Scholar
  12. 12.
    Abdel-Mageed WA, Bayoumi SAL, Al-wahaibi LH, Li L, Sayed HM, Abdelkader MSA, El-Gamal AA, Liu M, Zhang J, Zhang L, Liu X (2016) Noncyanogenic cyanoglucoside cyclooxygenase inhibitous from Simmondsia chinensis. Org Lett 18:1728–1731CrossRefGoogle Scholar
  13. 13.
    Sano T, Matsumura I, Nakamura R, Yamaji H, Hashimoto K, Takeda O, Kiuchi F, Takeda T (2010) Genetic and chemical comparison of Boi (Sinomenium Cauris et Rhizoma) and Seifuto (Caulis Sinomenii). J Nat Med 64:257–265CrossRefGoogle Scholar
  14. 14.
    Yogo M, Ishiguro S, Murata H, Furukawa H (1990) Coculauril, a nonglucosidic 2-cyclohexen-1-ylideneacetonitrile, from Cocculus lauriforius DC. Chem Pharm Bull 38:225–226CrossRefGoogle Scholar
  15. 15.
    Calveras J, Nagai Y, Sultana I, Ueda Y, Higashi T, Shoji M, Sugai T (2010) New chemo-enzymatic route toward N-acetylneuraminic acid derivatives with alkyl groups at C-7 hydroxyl group. Tetrahedron 66:4284–4291CrossRefGoogle Scholar
  16. 16.
    Tsunekawa R, Hanaya K, Higashibayashi S, Sugai T (2018) Synthesis of fisetin and 2′,4′,6′-trihydroxydihyrochalcone 4′-O-β-neohesperidoside based on site-selective deacetylation and deoxygenation. Biosci Biotechnol Biochem.  https://doi.org/10.1080/09168451.2018.1467263 Google Scholar
  17. 17.
    Ohtani I, Kusumi T, Kashman Y, Kakisawa H (1991) High-field FT-NMR application of Mosher’s method. The absolute configurations of marine terpenoids. J Am Chem Soc 113:4092–4096CrossRefGoogle Scholar
  18. 18.
    Kindler BLJ, Spiteller P (2007) Chemical defense of the crust Fungus Aleurodiscus amorphus by a tailor-maid cyanogenic cyanohydrin ether. Angew Chem Int Ed 46:8076–8078CrossRefGoogle Scholar
  19. 19.
    Ohara T, Makino F, Kondo K, Yamaji H, Endo Y, Sakakibara I, Terabayashi S, Aburada M (2004) Difference of constituent contents between Boi with white and black colors. In: Abstract papers of the 51st Annual Meeting of the Japanese Society of Pharmacognosy, p 225Google Scholar

Copyright information

© The Japanese Society of Pharmacognosy and Springer Japan KK, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Faculty of PharmacyKeio UniversityTokyoJapan

Personalised recommendations