柳珊瑚Leptogorgia rigida中甾体类成分研究
|
摘要
首次对南海柳珊瑚Leptogorgiarigida中甾体类次生代谢产物进行研究。采用硅胶柱柱层析、十八烷基硅烷键合硅胶填料、SephadexLH-20、高效液相色谱(HPLC)及薄层色谱(TLC)等多种方法进行分离纯化,通过核磁共振波谱(NMR)、质谱(MS)等现代波谱分析及物理常数对照等方法进行结构鉴定。从南海柳珊瑚Leptogorgiarigida次生代谢产物中分离得到8个甾类化合物,结构依次为:3β,6β,11-trihydroxy-9,11-seco-5α-chloest-7-en-9-one(1);3β,6α,11-trihydroxy-9,11-seco-5α-chloest-7-en-9-one(2);3β,6α,11-trihydroxy-5α-chloest-7,22(E)-dien-9-one(3);pregnan-4-en-3,20-dione(4);5α-pregnan-3,20-dione(5);3β-hydroxy-pregnan-5-en-20-dion(6);3β-hydroxy-5α-pregnan-20-one(7);和3β,6α, 11-trihydroxy-9, 11-seco-5α-gorgosterol (8)。所有化合物均首次从Leptogorgia属中得到。
Research was carried out on novel secondary metabolites from Leptogorgia rigida collected from the South China Sea. The secondary metabolites were isolated by silica gel column chromatography, ODS, Sephadex LH-20, thin layer chromatography, and high performance liquid chromatography(HPLC). The structures of compounds were identified by nuclear magnetic resonance spectrum(NMR), mass spectrum(MS), and literature analysis. Eight sterols were obtained and elucidated as follows: 3β, 6β, 11-trihydroxy-24-methyl-5α-chloest-9, 11-seco-7-en-9-one(1); 3β, 6α, 11-trihydroxy-24-methyl-5α-chloest-9, 11-seco-7-en-9-one(2); 3β, 6α, 11-tri-hydroxy-5α-chloest-9, 11-seco-7, 22(E)-dien-9-one(3); pregnan-4-en-3, 20-dione(4); 5α-pregnan-3, 20-dione(5); 3β-hydroxy-pregnan-5-en-20-dione(6); 3β-hydroxy-5α-pregnan-20-one(7); and Gorgosterol(8). All the sterols were first obtained from Leptogorgia rigida.
Research was carried out on novel secondary metabolites from Leptogorgia rigida collected from the South China Sea. The secondary metabolites were isolated by silica gel column chromatography, ODS, Sephadex LH-20, thin layer chromatography, and high performance liquid chromatography(HPLC). The structures of compounds were identified by nuclear magnetic resonance spectrum(NMR), mass spectrum(MS), and literature analysis. Eight sterols were obtained and elucidated as follows: 3β, 6β, 11-trihydroxy-24-methyl-5α-chloest-9, 11-seco-7-en-9-one(1); 3β, 6α, 11-trihydroxy-24-methyl-5α-chloest-9, 11-seco-7-en-9-one(2); 3β, 6α, 11-tri-hydroxy-5α-chloest-9, 11-seco-7, 22(E)-dien-9-one(3); pregnan-4-en-3, 20-dione(4); 5α-pregnan-3, 20-dione(5); 3β-hydroxy-pregnan-5-en-20-dione(6); 3β-hydroxy-5α-pregnan-20-one(7); and Gorgosterol(8). All the sterols were first obtained from Leptogorgia rigida.
引文
柴兴云,胡静,黄晖,等,2011.小月柳珊瑚中孕甾烷类的化学成分研究[J].热带海洋学报,30(1):127-130.CHAIXINGYUN,HU JING,HUANG HUI,et al,2011.Pregnane steroids from a gorgonian Menella sp.in South China Sea[J].Journal of Tropical Oceanography,30(1):127-130(in Chinese with English abstract).
柴兴云,唐力英,雷辉,等,2012.柳珊瑚化学成分与生物活性研究新进展[J].中国中药杂志,37(5):667-685.CHAIXINGYUN,TANG LIYING,LEI HUI,et al,2012.Most advance on chemical and biological investigations of gorgonian octocorals[J].China Journal of Chinese Materia Medica,37(5):667-685(in Chinese with English abstract).
高程海,方燕,易湘茜,等,2013.中国柳珊瑚萜类化合物研究新进展[J].广西科学院学报,29(2):108-113.GAOCHENGHAI,FANG YAN,YI XIANGXI,et al,2013.Advances in studies on terpenoids and their bioactivities from Gorgonian[J].Journal of Guangxi Academy of Sciences,29(2):108-113(in Chinese with English abstract).
刘虹,苏镜娱,曾陇梅,2004.豆荚软珊瑚Lobophyton sp.中的次生代谢产物研究[J].中山大学学报(自然科学版),43(1):122-124.LIU HONG,SU JINGYU,ZENG LONGMEI,2004.Studies on the secondary metabolites of the soft coral Lobophyton sp.[J].Acta Scientiarum Naturalium Universitatis Sunyatseni,43(1):122-124(in Chinese with English abstract).
欧云付,尹平河,徐石海,等,2011.南海圆形短指软珊瑚Sinularia Brassica的化学成分[J].光谱实验室,28(6):3293-3297.OU YUNFU,YIN PINGHE,XU SHIHAI,et al,2011.Chemical constituents in round short refers to soft coral Sinularia brassica from South China Sea[J].Chinese Journal of Spectroscopy Laboratory,28(6):3293-3297(in Chinese with English abstract).
温燕梅,漆淑华,张偲,2007.南海脆灯蕊柳珊瑚化学成分的研究[J].热带海洋学报,26(1):73-77.WEN YANMEI,QISHUHUA,ZHANG SI,2007.Studies on chemical constituents of gorgonian Junceella fragilis from South China Sea[J].Journal of Tropical Oceanography,26(1):73-77(in Chinese with English abstract).
AIELLO A,ESPOSITO G,FATTORUSSO E,et al,2003.Aplidiasterols A and B,two new cytotoxic 9,11-secosterols from the mediterranean ascidian Aplidium conicum[J].Steroids,68(9):719-723.
BLUNT J W,COPP B R,KEYZERS R A,et al,2014-2018.Marine natural products[J].Natural Product Reports,31(2):160-258,32(2):116-211,33(3):382-431,34(3):235-294,35(1):8-53.
BOONANANWONG S,KONGKATHIP B,KONGKATHIP N,2008.First synthesis of 3,16,20-polyoxygenated cholestanes,new cytotoxic steroids from the gorgonian Leptogorgia sarmentosa[J].Steroids,73(11):1123-1127.
CIMINO G,DE ROSA S,DE STEFANO S,et al,1984.C-18Hydroxy steroids from the Mediterranean gorgonian Leptogorgia sarmentosa[J].Experientia,40(3):246-248.
GARRIDO L,ZUBíA E,ORTEGA M J,et al,2000.Isolation and structure elucidation of new cytotoxic steroids from the gorgonian Leptogorgia sarmentosa[J].Steroids,65(2):85-88.
GUTIéRREZ M,CAPSON T L,GUZMáN H M,et al,2005.Leptolide,a new furanocembranolide diterpene from Leptogorgia alba[J].Journal of Natural Products,68(4):614-616.
KEYZERS R A,GRAY C A,SCHLEYER M H,et al,2006.Malonganenones A-C,novel tetraprenylated alkaloids from the Mozambique gorgonian Leptogorgia gilchristi[J].Tetrahedron,62(10):2200-2206.
KINGSLEY R J,CORCORAN M L,KRIDER K L,et al,2001.Thyroxine and vitamin D in the gorgonian Leptogorgia virgulata[J].Comparative Biochemistry and Physiology Part A:Molecular&Integrative Physiology,129(4):897-907.
KSEBATI M B,CIERESZKO L S,SCHMITZ F J.1984.11β,12β-Epoxypukalide,a furanocembranolide from the gorgonian Leptogorgia setacea[J].Journal of Natural Products,47(6):1009-1012.
LI YONGXIN,WU HUIXIAN,XU YING,et al,2013.Antifouling activity of secondary metabolites isolated from Chinese marine organisms[J].Marine Biotechnology,15(5):552-558.
LIU MIN,SHAO CHANGLUN,CHEN MIN,et al,2014.Bioactive 9,11-secosteroids from gorgonian Subergorgia suberosa collected from the South China Sea[J].Chemistry&Biodiversity,11(7):1109-1120.
MACNEVIN C J,ATIF F,SAYEED I,et al,2009.Development and screening of water-soluble analogues of progesterone and allopregnanolone in models of brain injury[J].Journal of Medicinal Chemistry,52(19):6012-6023.
MIRALLèS J,BARNATHAN G,GALONNIER R,et al,1995.New branched-chain fatty acids from the Senegalese gorgonian Leptogorgia piccola(white and yellow morphs)[J].Lipids,30(5):459-466.
MORITZ M I G,MAROSTICA L L,BIANCOéM,et al,2014.Polyoxygenated steroids from the octocoral Leptogorgia punicea and in vitro evaluation of their cytotoxic activity[J].Marine Drugs,12(12):5864-5880.
ORTEGA M J,ZUBíA E,SáNCHEZ M C,et al,2008.Cembrane diterpenes from the gorgonian Leptogorgia laxa[J].Journal of Natural Products,71(9):1637-1639.
PAULI G F,FRIESEN J B,G?DECKE T,et al,2010.Occurrence of progesterone and related animal steroids in two higher plants[J].Journal of Natural Products,73(3):338-345.
QI S H,ZHANG S,YANG L H,et al,2008.Antifouling and antibacterial compounds from the gorgonians Subergorgia suberosa and Scripearia gracillis[J].Natural Product Research,22(2):154-166.
SHINGATE B B,HAZRA B G,SALUNKE D B,et al,2011Stereoselective synthesis and antimicrobial activity of steroidal C-20 tertiary alcohols with thiazole/pyridine side chain[J].European Journal of Medicinal Chemistry,46(9):3681-3689.
VAN MINH C,CUONG N X,TUAN T A,et al,2007.A new9,11-secosterol from the Vietnamese sea soft coral,Sarcophyton mililatensis,increases the function of osteoblastic MC3T3-E1 cells[J].Natural Product Communications,2(11):1095-1100.
柴兴云,唐力英,雷辉,等,2012.柳珊瑚化学成分与生物活性研究新进展[J].中国中药杂志,37(5):667-685.CHAIXINGYUN,TANG LIYING,LEI HUI,et al,2012.Most advance on chemical and biological investigations of gorgonian octocorals[J].China Journal of Chinese Materia Medica,37(5):667-685(in Chinese with English abstract).
高程海,方燕,易湘茜,等,2013.中国柳珊瑚萜类化合物研究新进展[J].广西科学院学报,29(2):108-113.GAOCHENGHAI,FANG YAN,YI XIANGXI,et al,2013.Advances in studies on terpenoids and their bioactivities from Gorgonian[J].Journal of Guangxi Academy of Sciences,29(2):108-113(in Chinese with English abstract).
刘虹,苏镜娱,曾陇梅,2004.豆荚软珊瑚Lobophyton sp.中的次生代谢产物研究[J].中山大学学报(自然科学版),43(1):122-124.LIU HONG,SU JINGYU,ZENG LONGMEI,2004.Studies on the secondary metabolites of the soft coral Lobophyton sp.[J].Acta Scientiarum Naturalium Universitatis Sunyatseni,43(1):122-124(in Chinese with English abstract).
欧云付,尹平河,徐石海,等,2011.南海圆形短指软珊瑚Sinularia Brassica的化学成分[J].光谱实验室,28(6):3293-3297.OU YUNFU,YIN PINGHE,XU SHIHAI,et al,2011.Chemical constituents in round short refers to soft coral Sinularia brassica from South China Sea[J].Chinese Journal of Spectroscopy Laboratory,28(6):3293-3297(in Chinese with English abstract).
温燕梅,漆淑华,张偲,2007.南海脆灯蕊柳珊瑚化学成分的研究[J].热带海洋学报,26(1):73-77.WEN YANMEI,QISHUHUA,ZHANG SI,2007.Studies on chemical constituents of gorgonian Junceella fragilis from South China Sea[J].Journal of Tropical Oceanography,26(1):73-77(in Chinese with English abstract).
AIELLO A,ESPOSITO G,FATTORUSSO E,et al,2003.Aplidiasterols A and B,two new cytotoxic 9,11-secosterols from the mediterranean ascidian Aplidium conicum[J].Steroids,68(9):719-723.
BLUNT J W,COPP B R,KEYZERS R A,et al,2014-2018.Marine natural products[J].Natural Product Reports,31(2):160-258,32(2):116-211,33(3):382-431,34(3):235-294,35(1):8-53.
BOONANANWONG S,KONGKATHIP B,KONGKATHIP N,2008.First synthesis of 3,16,20-polyoxygenated cholestanes,new cytotoxic steroids from the gorgonian Leptogorgia sarmentosa[J].Steroids,73(11):1123-1127.
CIMINO G,DE ROSA S,DE STEFANO S,et al,1984.C-18Hydroxy steroids from the Mediterranean gorgonian Leptogorgia sarmentosa[J].Experientia,40(3):246-248.
GARRIDO L,ZUBíA E,ORTEGA M J,et al,2000.Isolation and structure elucidation of new cytotoxic steroids from the gorgonian Leptogorgia sarmentosa[J].Steroids,65(2):85-88.
GUTIéRREZ M,CAPSON T L,GUZMáN H M,et al,2005.Leptolide,a new furanocembranolide diterpene from Leptogorgia alba[J].Journal of Natural Products,68(4):614-616.
KEYZERS R A,GRAY C A,SCHLEYER M H,et al,2006.Malonganenones A-C,novel tetraprenylated alkaloids from the Mozambique gorgonian Leptogorgia gilchristi[J].Tetrahedron,62(10):2200-2206.
KINGSLEY R J,CORCORAN M L,KRIDER K L,et al,2001.Thyroxine and vitamin D in the gorgonian Leptogorgia virgulata[J].Comparative Biochemistry and Physiology Part A:Molecular&Integrative Physiology,129(4):897-907.
KSEBATI M B,CIERESZKO L S,SCHMITZ F J.1984.11β,12β-Epoxypukalide,a furanocembranolide from the gorgonian Leptogorgia setacea[J].Journal of Natural Products,47(6):1009-1012.
LI YONGXIN,WU HUIXIAN,XU YING,et al,2013.Antifouling activity of secondary metabolites isolated from Chinese marine organisms[J].Marine Biotechnology,15(5):552-558.
LIU MIN,SHAO CHANGLUN,CHEN MIN,et al,2014.Bioactive 9,11-secosteroids from gorgonian Subergorgia suberosa collected from the South China Sea[J].Chemistry&Biodiversity,11(7):1109-1120.
MACNEVIN C J,ATIF F,SAYEED I,et al,2009.Development and screening of water-soluble analogues of progesterone and allopregnanolone in models of brain injury[J].Journal of Medicinal Chemistry,52(19):6012-6023.
MIRALLèS J,BARNATHAN G,GALONNIER R,et al,1995.New branched-chain fatty acids from the Senegalese gorgonian Leptogorgia piccola(white and yellow morphs)[J].Lipids,30(5):459-466.
MORITZ M I G,MAROSTICA L L,BIANCOéM,et al,2014.Polyoxygenated steroids from the octocoral Leptogorgia punicea and in vitro evaluation of their cytotoxic activity[J].Marine Drugs,12(12):5864-5880.
ORTEGA M J,ZUBíA E,SáNCHEZ M C,et al,2008.Cembrane diterpenes from the gorgonian Leptogorgia laxa[J].Journal of Natural Products,71(9):1637-1639.
PAULI G F,FRIESEN J B,G?DECKE T,et al,2010.Occurrence of progesterone and related animal steroids in two higher plants[J].Journal of Natural Products,73(3):338-345.
QI S H,ZHANG S,YANG L H,et al,2008.Antifouling and antibacterial compounds from the gorgonians Subergorgia suberosa and Scripearia gracillis[J].Natural Product Research,22(2):154-166.
SHINGATE B B,HAZRA B G,SALUNKE D B,et al,2011Stereoselective synthesis and antimicrobial activity of steroidal C-20 tertiary alcohols with thiazole/pyridine side chain[J].European Journal of Medicinal Chemistry,46(9):3681-3689.
VAN MINH C,CUONG N X,TUAN T A,et al,2007.A new9,11-secosterol from the Vietnamese sea soft coral,Sarcophyton mililatensis,increases the function of osteoblastic MC3T3-E1 cells[J].Natural Product Communications,2(11):1095-1100.