苏铁的化学成分研究
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摘要
对苏铁(Cycas revoluta)的化学成分进行研究,采用多种色谱技术(硅胶、氧化铝和Sephadex LH-20等)从苏铁茎的乙酸乙酯部位分离得到16个化合物,其结构由HR-ESI-MS、1H和13CNMR等波谱学方法鉴定为5,6-去氢柳杉酚(1)、cunningine A (2)、6-羟基-5,6-去氢柳杉酚(3)、6α-羟基-7-氧代弥罗松酚(4)、ligballinol (5)、xanthoxyol (6)、callislignan A (7)、(2R,3R)-bis[(4-hydroxy-3-methoxyphenyl) methyl]-1,4-diacetate (8)、开环异落叶松脂醇(9)、二氢山柰酚(10)、4'-甲基木犀草素(11)、5-methoxypinosylvin (12)、N-benzoylphenyl alaninol(13)、(E,4R)-4-hydroxy-4,5,5-trimethyl-3-(3-oxobut-1-enyl) cyclohex-2-enone (14)、3-hydroxy-5α,6α-epoxy-β-io-none (15)和acuminantin (16)。以上化合物均为首次从苏铁属植物中分离得到,其中化合物13和16为首次以天然产物报道。本研究还首次发现了苏铁属植物中含有松香烷型二萜类(1～4)和芪类(12)化合物。化合物11具有中等的体外α-葡萄糖苷酶抑制活性。
Sixteen compounds were isolated from the stems of Cycas revoluta by various column chromatography involving silica gel,Al_2O_3,and Sephadex LH-20. Their structures were identified as 5,6-dehydrosugiol( 1),cunningine A( 2),6-hydroxy-5,6-dehydrosugiol( 3),6α-hydroxy-7-oxoferruginol( 4),ligballinol( 5),xanthoxyol( 6),callislignan A( 7),( 2 R,3 R)-bis[( 4-hydroxy-3-methoxyphenyl) methyl]-1,4-diacetate( 8),secoisolariciresinol( 9),dihydrokaempferol( 10),4'-methylluteolin( 11),5-methoxypinosylvin( 12),N-benzoylphenyl alaninol( 13),( E,4 R)-4-hydroxy-4,5,5-trimethyl-3-( 3-oxobut-1-enyl) cyclohex-2-enone( 14),3-hydroxy-5α,6α-epoxy-β-ionone( 15),and acuminantin( 16)based on HR-ESI-MS,1 H,and13 C NMR spectroscopic data. All the isolates were obtained from this genus for the first time,of which compounds 13 and 16 were firstly reported as the natural products. This is the first time to reveal abietanetype diterpenes( 1-4) and stilbene( 12) in this genus. Compound 11 showed moderate α-glucosidase inhibitory activity in vitro,with an inhibition rate of 52. 51 ± 2. 63 % at the concentration of 198. 00 μg/m L.
Sixteen compounds were isolated from the stems of Cycas revoluta by various column chromatography involving silica gel,Al_2O_3,and Sephadex LH-20. Their structures were identified as 5,6-dehydrosugiol( 1),cunningine A( 2),6-hydroxy-5,6-dehydrosugiol( 3),6α-hydroxy-7-oxoferruginol( 4),ligballinol( 5),xanthoxyol( 6),callislignan A( 7),( 2 R,3 R)-bis[( 4-hydroxy-3-methoxyphenyl) methyl]-1,4-diacetate( 8),secoisolariciresinol( 9),dihydrokaempferol( 10),4'-methylluteolin( 11),5-methoxypinosylvin( 12),N-benzoylphenyl alaninol( 13),( E,4 R)-4-hydroxy-4,5,5-trimethyl-3-( 3-oxobut-1-enyl) cyclohex-2-enone( 14),3-hydroxy-5α,6α-epoxy-β-ionone( 15),and acuminantin( 16)based on HR-ESI-MS,1 H,and13 C NMR spectroscopic data. All the isolates were obtained from this genus for the first time,of which compounds 13 and 16 were firstly reported as the natural products. This is the first time to reveal abietanetype diterpenes( 1-4) and stilbene( 12) in this genus. Compound 11 showed moderate α-glucosidase inhibitory activity in vitro,with an inhibition rate of 52. 51 ± 2. 63 % at the concentration of 198. 00 μg/m L.
引文
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2 Shi YH,Zhu HP,Yang PJ.Extraction and determination of flavonoids from leaves of Cycas revoluta[J].Modern Chin Med(中国现代中药),2015,17:125-129.
3 Moawad A,Hetta M,Zjawiony JK,et al.Phytochemical investigation of Cycas circinalis and Cycas revoluta leaflets:moderately active antibacterial bioflavonoids[J].Planta Med,2010,76:796-802.
4 Zhou Y,Zhang XR,Peng SL,et al.General outline of study on Cycas[J].World Sci Technol(世界科学技术),2001,3:47-50.
5 Tang Y,Liu MC,Li SL,et al.Screening and identification ofα-glucosidase inhibitors from Rhizoma coptidis extract using HPLC-DAD-MS[J].Nat Prod Res Dev(天然产物研究与开发),2016,28:1078-1083.
6 Fan L,Wang YL,Tang L.Review on screening methods forα-glucosidase inhibitors from natural resources[J].Nat Prod Res Dev(天然产物研究与开发),2016,28:313-321.
7 Luo JG,Ma L,Kong LY.New triterpenoid saponins with strongα-glucosidase inhibitory activity from the roots of Gypsophila oldhamiana[J].Bioorgan Med Chem,2008,16:2912-2920.
8 Chen XJ,Ni L,Bao MF,et al.Abietane diterpenoids from Cephalotaxus lanceolate[J].Nat Prod Res,2017,31:1-6.
9 Ye Y,Wang YP,Yao S,et al.The preparation method and application of abietane-type diterpenoids with serum lipidlowering activity(具有降血脂活性的松香烷型二萜类化合物,其制备方法及用途):CN 201510293425.0[P].2015-06-01.
10 Yao S,Tang CP,Ke CQ,et al.Abietane diterpenoids from the bark of Cryptomeria fortune[J].J Nat Prod,2008,71:1242.
11 Li A,She X,Zhang J,et al.Synthesis of C-7 oxidized abietane diterpenes from racemic ferruginyl methyl ether[J].Tetrahedron,2003,59:5737-5741.
12 Panthong K,Sompong R,Rukachaisirikul V,et al.Two new triterpenes and a new coumaroyl glucoside from the twigs of Mangifera foetida,Lour[J].Phytochem Lett,2015,11:43-48.
13 Lee DY,Seo KH,Jeong RH,et al.Anti-inflammatory lignans from the fruits of Acanthopanax sessiliflorus[J].Molecules,2012,18:41-49.
14 Rattanaburi S,Mahabusarakam W,Phongpaichit S,et al.Neolignans from Callistemon lanceolatus[J].Phytochem Lett,2012,5:18-21.
15 Yamauchi S,Nishiwaki H,Nakazaki S,et al.Structure-antifungal activity relationship of fluorinated dihydroguaiaretic acid derivatives and preventive activity against Alternaria alternata Japanese pear pathotype[J].J Agric Food Chem,2017,65:31.
16 Zeng XJ,Wang GC,Wu X,et al.Chemical constituents from Syringa pinnatifolia[J].Chin Tradit Herb Drugs(中草药),2013,44:1721-1725.
17 Li Q,Wang XG,Mo TX.Chemical constituents from radix and rhizome of Myrsine stolonifera[J].Chin Tradit Herb Drugs(中草药),2012,45:2904-2907.
18 Xu RL,Shi YP.Chemical constituents from Artemisiae anomalae[J].Chin Tradit Herb Drugs(中草药),2014,45:1521-1525.
19 Zhang YM,Gong QF,Yang JQ,et al.Antioxidant Constituents from Pinus massoniana(Pinaceae)[J].Plant Divers Resour(植物分类与资源学报),2013,35:209-215.
20 Su ZW,Ma ZH,Ye L,et al.N-containing phytochemicals from the seeds of Brucea javanica[J].Chem Nat Compd,2017,53:799-801.
21 Tao Y,Jiang W,Cheng YY,et al.Two new compounds from Senecio cannabifolius[J].J Asian Nat Prod Res,2012,14:826-830.
22 Kim I,Chin YW,Lim SW,et al.Norisoprenoids and hepatoprotective flavone glycosides from the aerial parts of Beta vulgaris var.cicla[J].Arch Pharm Res,2004,27:600-603.
23 Banerjee B,Roy SC.Concise enantioselective synthesis of furan lignans(-)-dihydrosesamin and(-)-acuminatin and furofuran lignans(-)-sesamin and(-)-methyl piperitol by radical cyclization of epoxides[J].Cheminform,2006,37:2913-2919.