Advanced
Diterpenoids from Leonurus japonicus
Diterpenoids from Leonurus japonicus
Journal of the Korean Chemical Society. 2015. Apr, 59(2): 179-182
Copyright © 2015, Korean Chemical Society
  • Received : December 11, 2014
  • Accepted : January 21, 2015
  • Published : April 20, 2015
Download
PDF
e-PUB
PubReader
PPT
Export by style
Article
Author
Metrics
Cited by
TagCloud
About the Authors
Hankui Wu
Sensheng Wang
Haijuan Liu
E Yan
Jinjin Wang
Xiangbei Wang
Wenchao Wei
Zhiyong Xu
Shanshan Sun
Yan Li
Ruijin Liu
Gang Li
Yunfeng Shi

Abstract
Keywords
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
PPT Slide
Lager Image
EXPERIMENTAL
- Reagents and Instruments
NMR spectra were recorded on a Bruker Avance III spectrometer operating at 400 MHz for 1 H and 100 MHz for 13 C. HRESIMS were measured with Waters UPLC-LCT Premier XE and was controlled by MassLynx 4.1 software. Optical rotations were acquired with a WZZ-2ss automatic polarimeter (Shanghai Shenguang High Strength Bolts Co., Ltd, China). Column chromatography was performed with silica gel (200-300 mesh, Yantai Institute of Chemical Technology, Yantai, China), Sephadex LH-20 (GE Healthcare). HPLC separation was performed on an instrument (LC-3000, Beijing Chuangxintongheng Science & Technology Co., Ltd, Beijing China) consisting of two pumps and a UV/Vis detector with an YMC-ODS-A (25×1 cm) semi-preparative column packed with C18 (5 μm). All organic solutions used were of analytical grade and purchased from Sinopharm Chemical Reagent Co., Ltd (Shanghai, China). Methanol used for HPLC was of HPLC-grade and purchased from Fisher Scientific Company (Fair Lawn, NJ, USA).
- Plant Material
The herb of L. japonicus was purchased from Zhangye, Gansu Province of China in March, 2014. It was identified by one of the authors (Dr. H. Wu). A voucher specimen (Code: hkwu-aynu-20140301) was deposited at the Pharmaceutical Research Lab, Anyang Normal University.
- Extraction and Isolation
The dried and powdered herb of L. japonicus (85 kg) was extracted with 95% EtOH (3 × 400 L) by percolation at room temperature. The solvent was evaporated under reduced pressure at 45 ℃ to yield 7.2 kg viscous syrup, which was dissolved in water and extracted with EtOAc to get 3 kg extract. The EtOAc fraction was suspended in 30% EtOH and allowed to pass through a column (30 cm × 100 cm) packed with AB-8 macroporous resin (10 kg), then eluted with 50%, 70%, 90%, and 95% EtOH to obtain fractions A-D. Fraction C (693 g) was separated by silica gel CC over petroleum ether-EtOAc (10:1) to get subfraction C1. The further separation of C1 with Sephadex LH-20 (MeOH) to yield a mixture rich in diterpenes (total diterpenoids). The total diterpenoids sample was purified by preparative HPLC. The mobile phase was a linear gradient of methanol (A) and H 2 O (B) as follows: methanol-water (methanol: 0−20 min, 85−98%; 20−22 min, 95−85%; 22−27 min, 85%). The flowrate was 4.0 ml min −1 , the injection volume was 200 mL for each run and the effluent was monitored at 215 nm by a UV detector. Peaks were collected manually, and the retention times for the isolates were 7.4 min ( 1 , 15 mg), 9.3 min ( 3 , 46 mg), 10.4 min ( 4 , 35 mg), 12.7 min ( 5 , 27 mg), and 15.1 min ( 2 , 18 mg) respectively. Identification of the HPLC peak fractions was performed by HRESIMS, 1 H and 13 C NMR, HMBC and HMQC technologies. The typical HPLC graph was shown in . 4 .
PPT Slide
Lager Image
HPLC separation of compounds 1−5.
Supporting Information. The 1 H and 13 C NMR, DEPT, HMQC, and HMBC spectra measured in CDCl 3 of new compounds 1−2 are provided.
Acknowledgements
This work was financially supported by Joint Fund for Fostering Talents of National Natural Science Foundation of China and Henan province (No. U1304825; U1204213), the National Natural Science Foundation of China (No. 201302004; 21304001; 21102005), the Foundation of the Ministry of Education of China for Returned Scholars (No. 2013.693).
References
Liu Z. K. , Wu D. R. , Shi Y. M. , Zeng T. , Liu S. H. , Du X. , Dang Y. J. , Xiao W. L. , Sun H. D. 2014 Chin. Chem. Lett. 25 677 -    DOI : 10.1016/j.cclet.2014.01.047
Romero-González R. R. , Avila-Núñez J. L. , Aubert L. , Alonso-Amelot M. E. 2006 Phytochemistry 67 965 -    DOI : 10.1016/j.phytochem.2006.03.015
Ye M. , Xiong J. , Zhu J. J. , Hong J. L. , Zhao Y. , Fan H. , Yang G. X. , Xia G. , Hu J. F. 2014 J. Nat. Prod. 77 178 -    DOI : 10.1021/np400838a
Fuchino H. , Daikonya A. , Kumagai T. , Goda Y. , Takahashi Y. , Kawahara N. 2013 Chem. Pharm. Bull. 61 497 -    DOI : 10.1248/cpb.c12-00670
Chang J. M. , Shen C. C. , Huang Y. L. , Shieh B. J. , Chen C. C. 2010 J. Asian Nat. Prod. Res. 12 740 -    DOI : 10.1080/10286020.2010.493712
Moon H. I. 2010 Phytother. Res 24 1256 -
Xiong L. , Peng C. , Zhou Q. M. , Wan F. , Xie X. F. , Guo L. , Li X. H. , He C. J. , Dai O. 2013 Molecules 18 963 -    DOI : 10.3390/molecules18010963
Zhang Y. , Deng S. , Qu L. , An Y. T. , Wu C. H. , Han L. F. , Gao X. M. , Wang T. 2013 Molecules 18 2967 -    DOI : 10.3390/molecules18032967
Xiong L. , Zhou Q. M. , Peng C. , Xie X. F. , Guo L. , Li X.H. , Liu J. , Liu Z. H. , Dai O. 2013 Molecules 18 5051 -    DOI : 10.3390/molecules18055051
Peng F. , Xiong L. , Zhao X. M. 2013 Molecules 18 13904 -    DOI : 10.3390/molecules181113904
Wu H. , Li J. , Fronczek F. R. , Ferreira D. , Burandt C.L. , Setola V. , Roth B. L. , Zjawiony J. K. 2013 Phytochemistry 91 229 -    DOI : 10.1016/j.phytochem.2012.02.021
Wu H. , Fronczek F. R. , Ferreira D. , Burandt C. L. , Zjawiony J. K. 2011 J. Nat. Prod. 74 831 -    DOI : 10.1021/np100956k
Li H. , Li M. M. , Su X. Q. , Sun J. , Gu Y. F. , Zeng K.W. , Zhang Q. , Zhao Y. F. , Ferreira D. , Zjawiony J. K. , Li J. , Tu P. F. 2014 J. Nat. Prod 77 1047 -    DOI : 10.1021/np5001329
Qin J. , Li H. M. , Gao L. , Liu D. , Li R. T. , Lee K. H. 2014 Phytochem. Lett. 10 313 -    DOI : 10.1016/j.phytol.2014.10.027
Rustaiyan A. , Mosslemin-Kupaii M. H. , Papastergiou F. , Jakupovic J. 1995 Phytochemistry 40 875 -    DOI : 10.1016/0031-9422(95)00344-7
Rodriguez B. , Savona G. 1980 Phytochemistry 19 1805 -    DOI : 10.1016/S0031-9422(00)83817-0
Fuchino H. , Daikonya A. , Kumagai T. , Goda Y. 2013 Chem. Pharm. Bull. 61 497 -    DOI : 10.1248/cpb.c12-00670
Narukawa F. , Niimura A. , Noguchi H. , Tamura H. , Kiuchi F. 2013 J. Nat. Med. 68 125 -