Citation: Qing-Lan Guo, Sheng Lin, Ya-Nan Wang, Cheng-Gen Zhu, Cheng-Bo Xu, Jian-Gong Shi. Gastrolatathioneine, an unusual ergothioneine derivative from an aqueous extract of “tian ma”: A natural product co-produced by plant and symbiotic fungus[J]. Chinese Chemical Letters, ;2016, 27(10): 1577-1581. doi: 10.1016/j.cclet.2016.06.040 shu

Gastrolatathioneine, an unusual ergothioneine derivative from an aqueous extract of “tian ma”: A natural product co-produced by plant and symbiotic fungus

State Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China

Corresponding author: Jian-Gong Shi, shijg@imm.ac.cn
Received Date: 3 June 2016
Revised Date: 14 June 2016
Accepted Date: 23 June 2016
Available Online: 1 October 2016

Figures(5)

Gastrolatathioneine (1), an unusual natural product derived from ergothioneine, a fungal amino acid containing an imidazole-2-thione moiety, was isolated from an aqueous extract of "tian ma" (the Gastrodia elata rhizomes). The structure of 1 including the absolute configuration was determined by extensive spectroscopic data analysis, combined with comparison of an experimental circular dichroism spectrum and calculated electronic circular dichroism spectra of stereoisomers, and confirmed by X-ray crystallography. The natural origin of 1 was proved by HPLC-ESIMS analysis of the crude extract. A biogenetic pathway of 1 is proposed on the basis of metabolic post-modification of ergothioneine that is biosynthesized by a symbiotic fungus. The plant and symbiotic fungus are co-producers of 1.
- Gastrodia elata,
- Orchidaceae,
- Ergothioneine,
- (+)-L-N,N-bis(4-hydroxybenzyl)ergothioneine,
- Gastrolatathioneine
1. [1]
  Jiangsu New Medical College, Dictionary of Traditional Chinese Medicine, Shanghai Science and Technology Publishing House, Shanghai, 1979, pp. 315-317.
2. [2]
  J. Zhou, X.Y. Pu, Y.B. Yang. Nine phenolic compounds of fresh Gastrodia elata Blume[J]. Chin. Sin. Bull., 1982,27:179-181.
3. [3]
  E.J. Shin, W.K. Whang, S. Kim. Parishin C attenuates phencyclidine-induced schizophrenia-like psychosis in mice:involvements of 5-HT1A receptor[J]. J. Pharmacol. Sci., 2010,113:404-408. doi: 10.1254/jphs.10040SC
4. [4]
  N.K. Huang, J.H. Lin, J.T. Lin. A new drug design targeting the adenosinergic system for Huntington's disease[J]. PLoS One, 2011,6e20934. doi: 10.1371/journal.pone.0020934
5. [5]
  K.Y. Kam, S.J. Yu, N. Jeong. p-Hydroxybenzyl alcohol prevents brain injury and behavioral impairment by activating Nrf2, PDI, and neurotrophic factor genes in a rat model of brain ischemia[J]. Mol. Cells, 2011,31:209-215. doi: 10.1007/s10059-011-0028-4
6. [6]
  X.M. Zhao, Y. Zou, H. Xu. Gastrodin protect primary cultured rat hippocampal neurons against amyloid-beta peptide-induced neurotoxicity via ERK1/2-Nrf2 pathway[J]. Brain Res., 2012,1482:13-21. doi: 10.1016/j.brainres.2012.09.010
7. [7]
  B.W. Kim, S. Koppula, J.W. Kim. Modulation of LPS-stimulated neuroinflammation in BV-2 microglia by Gastrodia elata:4-Hydroxybenzyl alcohol is the bioactive candidate[J]. J. Ethnopharmacol., 2012,139:549-557. doi: 10.1016/j.jep.2011.11.048
8. [8]
  W.D. Xu, Y. Tian, Q.L. Guo, Y.C. Yang, J.G. Shi. Secoeuphoractin, a minor diterpenoid with a new skeleton from Euphorbia micractina[J]. Chin. Chem. Lett., 2014,25:1531-1534. doi: 10.1016/j.cclet.2014.09.012
9. [9]
  Y. Tian, Q.L. Guo, W.D. Xu. A minor diterpenoid with a new 6/5/7/3 fusedring skeleton from Euphorbia micractina[J]. Org Lett, 2014,16:3950-3953. doi: 10.1021/ol501760h
10. [10]
  F. Wang, Y.P. Jiang, X.L. Wang. Aromatic glycosides from the flower buds of Lonicera japonica[J]. J. Asian Nat. Prod. Res., 2013,15:492-501. doi: 10.1080/10286020.2013.785531
11. [11]
  W.X. Song, Y.C. Yang, J.G. Shi. Two new β-hydroxy amino acid-coupled secoiridoids from the flower buds of Lonicera japonica:isolation, structure elucidation, semisynthesis, and biological activities[J]. Chin. Chem. Lett., 2014,25:1215-1219. doi: 10.1016/j.cclet.2014.05.037
12. [12]
  Z.B. Jiang, W.X. Song, J.G. Shi. Two new 1-(60-O-acyl-b-D-glucopyranosyl) pyridinium-3-carboxylates from the flower buds of Lonicera japonica[J]. Chin. Chem. Lett., 2015,26:69-72. doi: 10.1016/j.cclet.2014.10.011
13. [13]
  Y. Yu, Z.B. Jiang, W.X. Song. Glucosylated caffeoylquinic acid derivatives from the flower buds of Lonicera japonica[J]. Acta Pharm. Sinica B, 2015,5:210-214. doi: 10.1016/j.apsb.2015.01.012
14. [14]
  Y.F. Liu, M.H. Chen, X.L. Wang. Antiviral enantiomers of a bisindole alkaloid with a new carbon skeleton from the roots of Isatis indigotica[J]. Chin. Chem. Lett., 2015,26:931-936. doi: 10.1016/j.cclet.2015.05.052
15. [15]
  Y.F. Liu, M.H. Chen, Q.L. Guo. Antiviral glycosidic bisindole alkaloids from the roots of Isatis indigotica[J]. J. Asian Nat. Prod. Res., 2015,17:689-704. doi: 10.1080/10286020.2015.1055729
16. [16]
  Y.F. Liu, M.H. Chen, S. Lin. Indole alkaloid glucosides from the roots of Isatis indigotica[J]. J. Asian Nat. Prod. Res., 2016,18:1-12. doi: 10.1080/10286020.2015.1117452
17. [17]
  Y.F. Liu, X.L. Wang, M.H. Chen. Three pairs of alkaloid enantiomers from the root of Isatis indigotica[J]. Acta Pharm. Sinica B, 2016,6:141-147. doi: 10.1016/j.apsb.2016.01.003
18. [18]
  M.H. Chen, S. Lin, Y.N. Wang. Antiviral stereoisomers of 3,5-bis(2-hydroxybut-3-en-1-yl)-1,2,4-thiadiazole from the roots Isatis indigotica[J]. Chin. Chem. Lett., 2016,27:643-648. doi: 10.1016/j.cclet.2016.01.042
19. [19]
  Y.P. Jiang, Y.F. Liu, Q.L. Guo. Acetylenes and fatty acids from Codonopsis pilosula[J]. Acta Pharm. Sinica B, 2015,5:215-222. doi: 10.1016/j.apsb.2015.03.005
20. [20]
  Y.P. Jiang, Y.F. Liu, Q.L. Guo. C₁₄-Polyacetylene glucosides from Codonopsis pilosula, J. Asian Nat[J]. Prod. Res, 2015,17:601-614.
21. [21]
  Y.P. Jiang, Q.L. Guo, Y.F. Liu, J.G. Shi. Codonopiloneolignanin A, a polycyclic neolignan with a new carbon skeleton from the roots of Codonopsis pilosula, Chin[J]. Chem. Lett., 2016,27:55-58.
22. [22]
  Y.P. Jiang, Y.F. Liu, Q.L. Guo. Sesquiterpene glycosides from the roots of Codonopsis pilosula[J]. Acta Pharm. Sinica B, 2016,6:46-54. doi: 10.1016/j.apsb.2015.09.007
23. [23]
  Z.B. Jiang, B.Y. Jiang, C.G. Zhu. Aromatic acid derivatives from the lateral roots of Aconitum carmichaelii[J]. J. Asian Nat. Prod. Res., 2014,16:891-900. doi: 10.1080/10286020.2014.939585
24. [24]
  Z.B. Jiang, X.H. Meng, B.Y. Jiang. Two 2-(quinonylcarboxamino)benzoates from the lateral roots of Aconitum carmichaelii[J]. Chin. Chem. Lett., 2015,26:653-656. doi: 10.1016/j.cclet.2015.04.011
25. [25]
  Y.N. Wang, S. Lin, M.H. Chen. Chemical constituents from aqueous extract of Gastrodia elata, China[J]. J. Chin. Mater. Med., 2012,37:1775-1781.
26. [26]
  Q.L. Guo, Y.N. Wang, S. Lin. 4-Hydroxybenzyl-substituted amino acid derivatives from Gastrodia elata[J]. Acta Pharm. Sinica B, 2015,5:350-357. doi: 10.1016/j.apsb.2015.02.002
27. [27]
  Q.L. Guo, Y.N. Wang, C.G. Zhu. 4-Hydroxybenzyl-substituted glutathione derivatives from Gastrodia elata[J]. J. Asian Nat. Prod. Res, 2015,17:439-454. doi: 10.1080/10286020.2015.1040000
28. [28]
  Y. Zhang, M. Li, R.X. Kang. NHBA isolated from Gastrodia elata exerts sedative and hypnotic effects in sodium pentobarbital-treated mice[J]. Pharmacol. Biochem. Behav, 2012,102:450-457. doi: 10.1016/j.pbb.2012.06.002
29. [29]
  J.J. He, Z.G. Luo, L. Huang. Ambient mass spectrometry imaging metabolomics method provides novel insights into the action mechanism of drug candidates[J]. Anal. Chem., 2015,87:5372-5379. doi: 10.1021/acs.analchem.5b00680
30. [30]
  Spartan 10; Wavefunction, Inc., Irvine, CA.
31. [31]
  M.J. Frisch, G.W. Trucks, H.B. Schlegel, et al., Gaussian 09. Revision C. 01, Gaussian, Inc, Wallingford, CT, 2009.
32. [32]
  Bruker. SHELXTL. Structure Determination Programs, Version 5.10, Bruker AXS Inc., 6300 Enterprise Lane, Madison, WI 53719-1173, USA, 1997.
33. [33]
  C., M., K., Y. Sugawara, b-Hydroxyergothioneine, a new ergothioneine derivative from the mushroom Lyophyllum connatum, and its protective activity against carbon tetrachloride-induced injury in primary culture hepatocytes, Biosci[J]. Biotechnol. Biochem, 2005,69:357-363. doi: 10.1271/bbb.69.357
34. [34]
  X.C. Li, D. Ferreira, Y.Q. Ding. Determination of absolute configuration of natural products:theoretical calculation of electronic circular dichroism as a tool[J]. Curr. Org. Chem., 2010,14:1678-1697. doi: 10.2174/138527210792927717
35. [35]
  P. Fu, J.B. MacMillan. Spithioneines A and B, two new bohemamine derivatives possessing ergothioneine moiety from a marine-derived Streptomyces spinoverrucosus[J]. Org. Lett., 2015,17:3046-3049. doi: 10.1021/acs.orglett.5b01328
36. [36]
  C.E. Hand, J.F. Honek. Biological chemistry of naturally occurring thiols of microbial and marine origin[J]. J. Nat. Prod., 2005,68:293-308. doi: 10.1021/np049685x
37. [37]
  J. Ey, E. Schömig, D. Taubert. Dietary sources and antioxidant effects of ergothioneine[J]. J. Agric. Food Chem., 2007,55:6466-6474. doi: 10.1021/jf071328f
38. [38]
  D.S.L. Toh, F.S.G. Cheung, M. Murray. Functional analysis of novel variants in the organic cation/ergothioneine transporter 1 identified in Singapore populations[J]. Mol. Pharmaceutics, 2013,10:2509-2516. doi: 10.1021/mp400193r
39. [39]
  F.P. Seebeck. In vitro reconstitution of mycobacterial ergothioneine biosynthesis[J]. J. Am. Chem. Soc., 2010,132:6632-6633. doi: 10.1021/ja101721e
40. [40]
  W. Hu, H. Song, A.S. Her. Bioinformatic and biochemical characterizations of C S bond formation and cleavage enzymes in the Fungus Neurospora crassa ergothioneine biosynthetic pathway[J]. Org. Lett., 2014,16:5382-5385. doi: 10.1021/ol502596z
41. [41]
  D. Ackermann. P.H. List, Ü ber das vorkommen von herzynin, ergothionein, homarin, trigonellin, glykokollbetain, cholin, trimethylamin, adenin und fast sämtlicher aminosa üren des eiweißes in Limulus polyphemus[J]. L, Bio. Chem, 1958,313:30-36.
42. [42]
  H.X. Liu, Y.B. Luo, H. Liu. Studies of mycorrhizal fungi of Chinese orchids and their role in orchid conservation in China-a review[J]. Bot. Rev., 2010,76:241-262. doi: 10.1007/s12229-010-9045-9
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