裂萼苔水生变种化学成分
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摘要
目的分离并鉴定苔藓植物裂萼苔水生变种中的化学成分。方法利用MCI柱层析、硅胶柱层析、凝胶柱层析、半制备HPLC等技术手段对裂萼苔样品进行分离纯化,利用NMR、HRESIMS等波谱数据进行结构解析和鉴定。结果从该植物中分离得到5个化合物,包括2个新的桉烷型倍半萜,分别命名为(3S,7R,10S)-7-hydroxy-3-methoxy-eudesma-4E-ene(1)和(3S,7R,10S)-7-hydroxy-3-ethyoxyl-eudesma-4E-ene(2),1个愈创木烷型倍半萜(guaianediol,3),1个半日花烷型二萜(nivenolide,4)以及1个羽扇豆烷型三萜(betulin,5)。结论 1和2为新化合物, 3～5为首次从裂萼苔属植物中分离出来的已知化合物。
Objective To study the chemical constituents of Chiloscyphus polyanthus var.rivularis.Methods The chemical constituents were isolated and identified on the basis of various chromatographic methods such as MCI gel,silica gel,Sephadex LH-20 column,and semi-preparation HPLC as well as a combination of their spectroscopic data,such as NMR and HRESIMS.Results Isolation of Chiloscyphus polyanthus var.rivularis afforded five compounds,including two new eudesmane type sesquiterpenoids,which were named(3S,7R,10S)-7-hydroxy-3-methoxy-eudesma-4E-ene(1)and(3S,7R,10S)-7-hydroxy-3-ethyoxyl-eudesma-4E-ene(2),one guaiane type sesquiterpenoid(guaianediol,3),one labdanetype diterpenoid(nivenolide,4),and one triterpenoid(betulin,5).Conclusion Compounds 1 and 2 are previously undescribed and compounds 3-5 are isolated from the plants in genus Chiloscyphus for the first time.
Objective To study the chemical constituents of Chiloscyphus polyanthus var.rivularis.Methods The chemical constituents were isolated and identified on the basis of various chromatographic methods such as MCI gel,silica gel,Sephadex LH-20 column,and semi-preparation HPLC as well as a combination of their spectroscopic data,such as NMR and HRESIMS.Results Isolation of Chiloscyphus polyanthus var.rivularis afforded five compounds,including two new eudesmane type sesquiterpenoids,which were named(3S,7R,10S)-7-hydroxy-3-methoxy-eudesma-4E-ene(1)and(3S,7R,10S)-7-hydroxy-3-ethyoxyl-eudesma-4E-ene(2),one guaiane type sesquiterpenoid(guaianediol,3),one labdanetype diterpenoid(nivenolide,4),and one triterpenoid(betulin,5).Conclusion Compounds 1 and 2 are previously undescribed and compounds 3-5 are isolated from the plants in genus Chiloscyphus for the first time.
引文
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[22]Xie CF, Sun B, Guo DX, et al. Terpenoids from the Chinese liverwort chiloscyphus polyanthus[J]. HCA, 2011, 94(3): 534-538.
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[24]Zhang JZ, Wang YJ, Zhu RX, et al. Cyperane and eudesmane-type sesquiterpenoids from Chinese liverwort and their anti-diabetic nephropathy potential[J]. RSC Adv, 2018, 8(68): 39091-39097.
[25]Wu C, Gunatilaka AA, McCabe FL, et al. Bioactive and other sesquiterpenes from Chiloscyphus rivularis[J]. J Nat Prod, 1997, 60(12): 1281-1286.
[26]Harrison LJ, Asakawa Y. Oppositane and chiloscyphane sesquiterpenoids from the liverwort Chiloscyphus pallescens[J]. Phytochemistry, 1991, 30(11): 3806-3807.
[27]Cullmann F, Schmidt A, Schuld F, et al. Lignans from the liverworts Lepidozia incurvata, Chiloscyphus polyanthos and Jungermannia exsertifolia ssp. cordifolia[J]. Phytochemistry, 1999, 52(8): 1647-1650.
[28]Asakawa Y. Chemosystematics of the hepaticae[J]. Phytochemistry, 2004, 65(6): 623-669.
[2]Bowman JL, Kohchi T, Yamato KT, et al. Insights into land plant evolution garnered from the marchantia polymorpha genome[J]. Cell, 2017, 171(2): 287-304.e15.
[3]吴鹏程. 苔藓植物生物学[M]. 北京: 科学出版社, 1998.
[4]娄红祥. 苔藓植物化学与生物学[M]. 北京: 北京科学技术出版社, 2006.
[5]Asakawa Y, Ludwiczuk A. Chemical constituents of bryophytes: structures and biological activity[J]. J Nat Prod, 2018, 81(3): 641-660.
[6]Asakawa Y, Ludwiczuk A, Nagashima F. Phytochemical and biological studies of bryophytes[J]. Phytochemistry, 2013, 91: 52-80. doi:10.1016/j.phytochem.2012.04.012.
[7]Asakawa Y. Biologically active compounds from bryophytes[J]. Pure and Applied Chemistry, 2007, 79(4): 557-580.
[8]Zinsmeister HD, Becker H, Eicher T. Bryophytes, a source of biologically active, naturally occurring material?[J]. Angew Chem Int Ed Engl, 1991, 30(2): 130-147.
[9]Guo DX, Zhu RX, Wang XN, et al. Scaparvin A, a novel caged cis-clerodane with an unprecedented C-6/C-11 bond, and related diterpenoids from the liverwort Scapania parva[J]. Org Lett, 2010, 12(19): 4404-4407.
[10]Wang LN, Zhang JZ, Li X, et al. Pallambins A and B, unprecedented hexacyclic 19-nor-secolabdane diterpenoids from the Chinese liverwort Pallavicinia ambigua[J]. Org Lett, 2012, 14(4): 1102-1105.
[11]Zhou JC, Zhang JZ, Cheng AX, et al. Highly rigid labdane-type diterpenoids from a Chinese liverwort and light-driven structure diversification[J]. Org Lett, 2015, 17(14): 3560-3563.
[12]Zhou JC, Zhang JZ, Li RJ, et al. Hapmnioides A-C, rearranged labdane-type diterpenoids from the Chinese liverwort haplomitrium mnioides[J]. Org Lett, 2016, 18(17): 4274-4276.
[13]Han JJ, Zhang JZ, Zhu RX, et al. Plagiochianins A and B, two ent-2, 3-seco-aromadendrane derivatives from the liverwort Plagiochila duthiana[J]. Org Lett, 2018, 20(20): 6550-6553.
[14]Wang YY, Wang LN, Hu ZY, et al. A novel derivative of riccardin D induces cell death through lysosomal rupture in vitro and inhibits tumor growth in vivo[J]. Cancer Lett, 2013, 329(2): 207-216.
[15]Lin ZM, Guo YX, Gao YH, et al. Ent-kaurane diterpenoids from Chinese liverworts and their antitumor activities through michael addition as detected in situ by a fluorescence probe[J]. J Med Chem, 2015, 58(9): 3944-3956.
[16]el Sayed KA, Hamann MT. A new norcembranoid dimer from the red sea soft coral Sinularia gardineri[J]. J Nat Prod, 1996, 59(7): 687-689.
[17]Rojas ET, Rodriguez-Hahn L. Nivenolide, a diterpene lactone from Croton niveus[J]. Phytochemistry, 1978, 17(3): 574-575.
[18]王晓林, 李良琼, 李美蓉. 扁枝槲寄生化学成分研究(Ⅲ)[J]. 华西药学杂志, 1995, 10(1): 1-3. WANG Xiaolin, LI Liangqiong, LI Meirong. Studies on the chemical constituents of Viscum articulatum Burm.f. (Ⅲ)[J]. West China Journal of Pharmaceutcal Sciences, 1995, 10(1): 1-3.
[19]高谦.中国苔藓志[M]. 9卷.北京: 科学出版社, 2003.
[20]Ma B, Lu ZQ, Guo HF, et al. Rearranged calamenene and eudesmane sesquiterpenoids from two Chinese liverworts[J]. HCA, 2007, 90(1): 52-57.
[21]Toyota M, Saito T, Asakawa Y. The absolute configuration of eudesmane-type sesquiterpenoids found in the Japanese liverwort Chiloscyphus polyanthos[J]. Phytochemistry, 1999, 51(7): 913-920.
[22]Xie CF, Sun B, Guo DX, et al. Terpenoids from the Chinese liverwort chiloscyphus polyanthus[J]. HCA, 2011, 94(3): 534-538.
[23]Zhang JZ, Qiao YN, Li L, et al. Ent-eudesmane-type sesquiterpenoids from the Chinese liverwort chiloscyphus polyanthus var. rivularis[J]. Planta Med, 2016, 82(11/12): 1128-1133.
[24]Zhang JZ, Wang YJ, Zhu RX, et al. Cyperane and eudesmane-type sesquiterpenoids from Chinese liverwort and their anti-diabetic nephropathy potential[J]. RSC Adv, 2018, 8(68): 39091-39097.
[25]Wu C, Gunatilaka AA, McCabe FL, et al. Bioactive and other sesquiterpenes from Chiloscyphus rivularis[J]. J Nat Prod, 1997, 60(12): 1281-1286.
[26]Harrison LJ, Asakawa Y. Oppositane and chiloscyphane sesquiterpenoids from the liverwort Chiloscyphus pallescens[J]. Phytochemistry, 1991, 30(11): 3806-3807.
[27]Cullmann F, Schmidt A, Schuld F, et al. Lignans from the liverworts Lepidozia incurvata, Chiloscyphus polyanthos and Jungermannia exsertifolia ssp. cordifolia[J]. Phytochemistry, 1999, 52(8): 1647-1650.
[28]Asakawa Y. Chemosystematics of the hepaticae[J]. Phytochemistry, 2004, 65(6): 623-669.