通光藤甙元甲、乙和丙的结构——悼念蔡希陶教授

通光藤〔Marsdenia tenacissima（Roxb.）Wight et Arn.〕系云南民间治疗气管炎和抗癌药用植物。前报我们报告了通光藤甙元甲的结构的部分研究工作。自分离甙元甲的母液中我们又分得了两个少量新甙元——通光藤甙元乙和丙（tenacigenin B and C）。本文报告它们的结构研究,并在此基础上对前报所推定的通光藤甙元甲的六元氧环的立体构型提出修正。     

美飞蛾藤（Porana spectabilis Kurz）植物中的化学成分

首次从旋花科飞蛾藤属植物美飞蛾藤（Porana spectabilis Kurz)醇提物中分离鉴定了8个已知化合物,通过波谱方法确定了它们的结构分别为东莨菪素（7－hydroxy-6-methoxycoumarin or soopoletin)(1),东莨菪甙（scoplin)(2);咖啡酸乙酯（ethyl caffeate)(3)和3,5－二羟基肉桂酸（3－（3,5－dihydroxyphenyl)-2E-propenoic acid)(4);α－（D）－甲基呋喃果糖甙（Methylα-Dfrucofuranoside)(5)β－（D）－甲基吡喃果糖甙（Methyl β－D-frucopyranoside)(6);2,5-二羟基基苯甲酸（2,5－dihydroxybenzoic acid)(7);丁香脂素－4－O－β－D－吡喃葡萄糖甙（＋）syringaresinol-4-O-β-(D)-glucopyranoside)(8)。     

云南匙羹藤的化学成分

从云南匙羹藤(Gymnema yunnanense Tsiang)的粗甙酸水解产物中分离得到6个C_(21)甾体甙元。其中一个新甙元,命名为吉马甙元(gymnemarsgenin),经光谱数据和化学反应证明其结构为12-β-氧-苯甲酰-20-氧-肉桂珊瑚甙元。     

云南匙羮藤甙A和B的结构

从云南匙羹藤(Gymnema yunnaflense Tsiang)中分离得到2个新C_(21)甾体甙,命名为云南匙羹藤甙A(Ⅰ)和B(Ⅱ)(gymnemaroside A, B)。据化学反应和光谱数据,推定其结构分别为:本波甙元3-氧-β-D-葡萄糖吡喃基-(1→4)-3-氧-甲基-6-去氧-β-D阿洛糖吡喃基-(1→4)-β-D-加拿大麻糖吡喃基-(1→4)-β-D-加拿大麻糖吡喃甙〔penupogenin 3-O-β-D-glucopyranosyl-(1→4)-3-O-methyl-6-deoxy-β-D-allopyranosyl-(1→4)-β-D-cymaropyranosyl-(1→4)-β-D-cymaropyranoside〕和吉马甙元3-氧-β-D-葡萄糖吡喃基-(1→4)-3-氧-甲基-6-去氧-β-D-阿洛糖吡喃基-(1→4)-β-D-加拿大麻糖吡喃基-(1→4)-β-D-加拿大麻糖吡喃甙〔symnemarsgenm 3-O-β-D-glucopyranosyl-(1→4)-3-O-methyl-6-deoxy-β-D-allopyranosyl-(1→4)-β-D-cymaropyranosyl-(1→d)-β-D-cymaropyranoside〕。     

红叶藤化学成分的研究

从红叶藤[Rourea microphylla(Hook.et Arn)Plan ch.]茎叶中分得11种化合物,经理化常数测定、光谱分析及化学方法鉴定为槲皮素-3-O-α-L-鼠李吡喃糖甙(Ⅰ)、金丝桃甙(Ⅱ),槲皮素(Ⅲ)、落新妇甙(Ⅳ)、β-谷甾醇(Ⅴ)、β-谷甾醇-β-D-葡萄吡喃糖甙(Ⅵ)、大黄素甲醚(ⅦI)、红灰青素(Ⅷ)、硬脂酸(Ⅸ)、软脂酸(Ⅹ)和正九烷(Ⅺ)。其中化合物Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅵ、Ⅶ、Ⅷ、Ⅸ、Ⅹ和Ⅺ为首次。从红叶藤属植物中分得。     

蚁花的化学成分研究

从蚁花（Mezzettiopsis creaghii Ridl.）枝叶的乙醇提取物首次分离得到6个化合物,通过波谱分析分别鉴定为liriodenine(Ⅰ）,oxoputerine(Ⅱ),liriodendronine(Ⅲ),conocarpan(Ⅳ),菠萝香藤甙甲（Ⅴ）和（3S,5R,6S,9R）－3,6－二羟基－5,6－二氢－β-紫萝醇（Ⅵ ）。     

响应面法优化乌骨藤通光藤苷G提取工艺

利用响应面法对乌骨藤Marsdenia tenacissima通光藤苷G的提取工艺进行优化。以通光藤苷G提取率为指标,在单因素试验的基础上,选取乙醇浓度、料液比、提取时间、提取次数进行4因素3水平的Box-Behnken中心组合研究,并运用Design Expect 8.0软件对试验参数进行分析,研究各自变量及其交互作用对通光藤苷G提取率的影响。结果显示,通光藤苷G的最佳提取条件为：乙醇溶液浓度80%,料液比1∶20(W/V),提取时间1.5 h,提取2次,在此条件下,通光藤苷G提取率为0.253%。     

茉莉花的化学成分

从药用植物茉莉花(Jasminum sambac(L．)Ait．)花蕾中分离到9个化合物,通过波谱分析并与已知化合物数据对照,分别鉴定为：苄基-O-β-D-葡萄吡喃糖甙(1),苄基-O-β-D-木吡喃糖基(1→6)-β-D-葡萄吡喃糖甙(2),tetraol(3),molihuaoside D(4),sarnhcoside A(5),sambacoside E(6),芦丁(rutin)(7),山奈酚-3-O-α-L鼠李吡喃糖基(1-2)[α-L鼠李吡喃糖基(1-6)]-β-D半乳吡喃糖甙(8),斛皮素-3-O-α-L鼠李吡喃糖基(1→2)[α-L鼠李吡喃糖基(1→6)]-β-D-半乳吡喃糖甙(9)。     

思茅藤的化学成分研究

从思茅藤(Epigynum auritum (schneid.)Tsiang et P.T.Li)的茎皮中分离到一个新的化合物,命名为思茅藤甙(Epigcoside)Ⅰ和已知化合物Ⅱ。通过光谱分析和化学反应证明,其结构为Ⅰ(+)—儿茶素-3-O-α-D-葡萄吡喃糖(1→6)-β-D葡萄吡喃糖甙((+)-catchin—3-O-α-D-glucopyranosyl-(1→6)-β—D-glucopyranoside;Ⅱβ-谷甾醇β-D-葡萄糖甙(β-sitosterol-β-D-glucoside)。     

攀枝花苏铁叶中的一个新黄酮碳甙

从攀枝花苏铁(Cycas panzhihuaensis L. Zhou et S. Y. Yang)叶中分离出6个化合物,其中1个为新黄酮碳甙,命名为攀枝花苏铁甙(1),其结构通过波谱解析和化学降解得以确定.其余化合物分别鉴定为2,3-二氢偏柏黄酮(2)、 5,5″,7,7″,4′,4-六羟基-(2′,8″)-双黄酮(3)、香草酸(4)、β-谷甾醇(5)和胡萝卜甙(6).     

Four new immunomodulating steroidal glycosides from the stems of Stephanotis mucronata

Four new C-21 steroidal glycosides, mucronatosides E (1), F (2), G (3), and H (4), were isolated from the stems of Stephanotis mucronata. Two of them had the rare aglycone with a double bond between C-6 and C-7. Their structures were elucidated on the basis of spectroscopic data and chemical evidence. These isolated compounds were assayed for their immunological activities in vitro against concanavalin A (Con A)- and lipopolysaccharide (LPS)-induced proliferation of mice splenocytes. Compounds 2 and 4 showed immunosuppressive activities in a dose-dependent manner, while compounds 1 and 3 possessed immunoenhancing activities.     

New steroidal glycosides from rhizomes of Clintonia udensis

A total of 10 steroidal glycosides, together with three new spirostanol glycosides (6-8), a new furostanol glycoside (9), and a new cholestane glycoside (10), were isolated from the rhizomes of Clintonia udensis (Liliaceae). The structures of the new compounds were determined on the basis of extensive spectroscopic analyses, including 2-D nuclear magnetic resonance (NMR) data, and of hydrolytic cleavage followed by chromatographic or spectroscopic analyses. The isolated glycosides were evaluated for their cytotoxic activity against HL-60 leukemia cells. Spirostanol glycosides 1 and 2, and furostanol glycoside 4 showed cytotoxic activity with IC(50) values of 3.2+/-0.02, 2.2+/-0.12, and 2.2+/-0.06 microg/ml, respectively. Neither the spirostanol and furostanol saponins with a hydroxy group at C-1 (6 and 9) and C-12 (7 and 8) nor cholestane glycosides (5 and 10) exhibited apparent cytotoxic activity at a sample concentration of 10 microg/ml.     

New pregnane glycosides from Stelmatocrypton khasianum

Four new pregnane glycosides, stelmatocryptonoside A, B, C, and D (1-4), were isolated from the stems of Stelmatocrypton khasianum. On the basis of chemical and spectral data, the structures of 1-4 were established as 3beta, 16alpha-dihydroxy-pregn-5-en-20-one-16-O-beta-D-glucopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->6)]-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside; 3beta, 20-dihydroxy-pregn-5-en-20-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->2)-beta-D-digitalopyranoside; 3beta, 16alpha-dihydroxy-pregn-5-en-20-one-16-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside; and 3beta, 16alpha-dihydroxy-pregn-5-en-20-one-16-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside. This is the first report of pregnane glycosides with sugar chains linked at C-16 of the aglycone.     

Specificity of chicken liver carbohydrate binding protein

Chicken hepatic lectin was isolated with affinity chromatography by using neoglycoproteins of bovine serum albumin (BSA) to which n moles of glycosides has been attached by amidination (Glycn-AI-BSA) [Lee, Y. C., Stowell, C. P., & Krantz, M. J. (1976) Biochemistry 15, 3956-3963] attached to Sepharose 4B. The same protein could be isolated from Man-, GlcNAc-, and Glc-AI-BSA-Sepharose columns and was identical with the protein previously reported [Kawasaki, T., & Ashwell, G. (1977) J. Biol. Chem. 252, 6536-6543]. The sugar specificity for binding to the isolated chicken hepatic lectin examined with Glycn-AI-BSA showed the order of potency for binding Glycn-AI-BSA to be D-GlcNAc greater than D-Glc, D-Man, L-Fuc greater than D-Gal, and the estimated Ki's for binding GlcNAc36-AI-BSA, Glc37-AI-BSA, Man33-AI-BSA, and L-Fuc28-AI-BSA were (6-20) X 10(-11), (2-3) X 10(-8), (3-9) X 10(-8), and 5 X 10(-8) M, respectively. The binding requirements of the binding protein were studied with a wide variety of Glycn-BSA's with different sugars and aglyconic linkages, as well as simple sugars and glycosides. It was concluded that (1) GlcNAc is the most potent sugar for binding, (2) the requirement for C-2 substituents is flexible, (3) an equatorial OH group at C-3 and C-4 must be present, (4) the 5-CH2OH group is not required for binding, (5) the lectin cannot accommodate a negative charge at C-6, and (6) D-Man and L-Fuc bind equally well.(ABSTRACT TRUNCATED AT 250 WORDS)     

Concise syntheses of arabinogalactans with beta-(1-->6)-linked galactopyranose backbones and alpha-(1-->3)- and alpha-(1-->2)-linked arabinofuranose side chains

4-methoxyphenyl glycosides of 2,3'-bis-alpha-L-arabinofuranosyl branched beta-D-(1-->6)-linked galactopyranosyl tetraose (16), 3',2'-bis-alpha-L-arabinofuranosyl branched beta-D-(1-->6)-linked galactopyranosyl hexaose (27), and a twentyose (42) consisting of beta-(1-->6)-linked D-galactopyranosyl pentadecaoligosaccharide backbone with alpha-L-arabinofuranosyl side chains alternately attached at C-2 and C-3 of the middle galactose residue of each consecutive beta-(1-->6)-linked galactotriose unit of the backbone, were synthesized with isopropyl 3-O-allyl-2,4-di-O-benzoyl-1-thio-beta-D-galactopyranoside (6), 2,3,4,6-tetra-O-benzoyl-alpha-D-galactopyranosyl trichloroacetimidate (7), 2,3,5-tri-O-benzoyl-alpha-L-arabinofuranosyl trichloroacetimidate (12), 6-O-acetyl-2,3,4-tri-O-benzoyl-alpha-D-galactopyranosyl trichloroacetimidate (17), 4-methoxyphenyl 2,3,4-tri-O-benzoyl-beta-D-galactopyranoside (19), and 2,6-di-O-acetyl-3,4-di-O-benzoyl-alpha-D-galactopyranosyl trichloroacetimidate (28) as the key synthons. Condensation of 6 with 7 gave the disaccharide donor 8, and subsequent condensation of 8 with 4-methoxyphenyl 2,3,4-tri-O-benzoyl-beta-D-galactopyranosyl-(1-->6)-2-O-acetyl-3,4-di-O-benzoyl-beta-D-galactopyranoside (9) followed by selective deacetylation afforded the tetrasaccharide acceptor 11. Coupling of 11 with 12 gave the pentasaccharide 13, its deallylation followed by coupling with 12, and debenzoylation gave the hexasaccharide 16 with beta-(1-->6)-linked galactopyranose backbone and 2- and 3'-linked alpha-L-arabinofuranose side chains. The octasaccharide 27 was similarly synthesized, while the twentyoside 42 was synthesized with tetrasaccharides 33 or 24 as the donors and 23, 36, 38, and 40 as the acceptors by consecutive couplings followed by deacylation.     

Identification of new qingyangshengenin and caudatin glycosides from the roots of Cynanchum otophyllum

HPLC analysis of the roots of Cynanchum otophyllum Scheind (Asclepiadaceae) led to the isolation of six new pregnane glycosides, specifically otophyllosides N-P (2-4) and otophyllosides Q-S (7-9), in addition to the identification of three known C-21 steroidal glycosides, otophylloside A (1), otophylloside B (5) and caudatin 3-O-β-D-glucopyranosyl-(1→4)-β-D-oleandropyranosyl-(1→4)-β-D-cymaropyranosyl-(1→4)-β-D-cymaropyranoside (6). The structure of each glycoside was determined by detailed spectroscopic analysis and chemical methods. All compounds contain qingyangshengenin or caudatin aglycones and a straight sugar chain consisting of 4-7 hexosyl moieties with the mode of 1→4 linkage. The optically isomeric monosaccharides, D- and L-cymarose, coexisted in both otophyllosides R (8) and S (9).     

Mode of cleavage of the c-c bonds in methyl pento- and hexo-pyranosides with periodate

The course of oxidation reactions of three methyl pentopyranosides and five methyl hexopyranosides with periodate was studied by simultaneous determination of the conjugated aldehydes in the products. It was found that the C-3-C-4 bonds in all of these glycosides were cleaved rapidly, but the velocity of subsequent cleavage of the C-2-C-3 bonds depended on the configuration of the substituent groups on the pyranose ring. Equatorial C-1 methoxyl and C-2 hydroxyl groups favored cleavage of the C-2-C-3 bonds more than did the corresponding axial groups, whereas the equatorial C-5 hydroxymethyl group suppressed C-2-C-3-bond-cleavage. The 4-isomeric glycosides were oxidized at the same rate, without regard to the configuration at C-4.     

New pregnane glycosides from the roots of Cynanchum otophyllum

Six new pregnane glycosides with an acyl at C-12 and a straight sugar chain at C-3, namely otophyllosides H-M (1-6), were isolated from the roots of Cynanchum otophyllum (Asclepiadaceae) collected from Eryuan County in Yunnan province of China. Their structures were characterized to be qingyangshengenin 3-O-beta-d-glucopyranosyl-(1-->4)-beta-d-glucopyranosyl-(1-->4)-beta-d-cymaropyranosyl-(1-->4)-beta-d-oleandropyranosyl-(1-->4)-beta-d-digitoxopyranoside (1), qingyangshengenin 3-O-beta-d-glucopyranosyl-(1-->4)-beta-d-oleandropyranosyl-(1-->4)-beta-d-cymaropyranosyl-(1-->4)-beta-d-digitoxopyranoside (2), qingyangshengenin 3-O-beta-d-glucopyranosyl-(1-->4)-beta-d-cymaropyranosyl-(1-->4)-beta-d-oleandropyranosyl-(1-->4)-beta-d-cymaropyranosyl-(1-->4)-beta-d-digitoxopyranoside (3), qingyangshengenin 3-O-beta-d-glucopyranosyl-(1-->4)-beta-d-thevetopyranosyl-(1-->4)-beta-d-cymaropyranosyl-(1-->4)-beta-d-digitoxopyranoside (4), caudatin 3-O-beta-d-glucopyranosyl-(1-->4)-beta-d-glucopyranosyl-(1-->4)-beta-d-cymaropyranosyl-(1-->4)-beta-d-oleandropyranosyl-(1-->4)-beta-d-cymaropyranoside (5), caudatin 3-O-beta-d-glucopyranosyl-(1-->4)-beta-d-cymaropyranosyl-(1-->4)-beta-d-oleandropyranosyl-(1-->4)-beta-d-cymaropyranosyl-(1-->4)-beta-d-cymaropyranoside (6), respectively, on the basis of detailed spectroscopic analysis and chemical method.     

The use of 1-O-sulfonyl-d-mannopyranose derivatives in β-d-mannopyranoside synthesis

Several 1-O-sulfonyl derivatives of d-mannopyranose having a nonparticipating benzyl ether group at C-2 and ester functions at C-6 and C-4 were synthesized from the corresponding d-mannopyranosyl chloride derivatives with silver sulfonates in acetonitrile. The reaction of 1-O-sulfonyl-d-mannopyranose compounds with methanol in various solvents at room temperature gave high yields of glycosides with low degrees of stercoselectivity. On the other hand, 1-O-suffonyl-d-mannopyranose derivatives having an acyl participating-group at O-2 and benzyl ethers at C-3, C-4, and C-6 gave high yields and high stereoselectivity of α-d-mannopyranosides with primary and secondary alcohols in several solvents. Model studies were carried out to determine the best combination of 2-O-acyl group, solvent, time, temperature, and 1-O-sufonyl group to give high yields with high stereoselectivity. The method has been used to prepare in good yields more complex glycosides, including perbenzylated methy 2-O-(α-d-mannopyranosyl)-α-d-mannopyranoside.     

Two γ-Methyl Biosides from Dregea volubilis (L.) Benth

From the hydrolysate of the crude glycosides from the roots, of Dregea volubilis(L.) Benth in Dehong, Yunnan, two α-methyl biosides Ⅰ and Ⅱ (yields: 0.016%and 0.0097%, respectively) were isolated by silica gel column chromatography. Theirchemical structures were established by interpretation of MS, IR,1H,13C-NMR, andgas chromatographic analysis of their degradation products, and comparison of thephysical properties of Ⅰ, Ⅱ and their acetates which were reported in literatures asfollows: α-methyl-pachybioside for Ⅰ, and α-methyl-[3-O-methyl-6-deoxy-D-allose(1→4)-D-olivoside] for Ⅱ. Ⅱ named α-methyl-dredehongbioside, is reported for the first time. Ⅱ, α-methyl-dredehongbioside, colorless needles (from MeOH), bitter, mp. 184–186℃,[α]D22 +74.5˚~(c= 0.52, MeOH). Anal. Cald(%) for C14H26O8:C52.17, H8.07;Found; C52.23,H8.22. Irvmaxkbr: 3370, 1443, 1419, 1375, 1268, 1218, 1168,1127,1060cm-1. MS(m/e,%): 322(M+,3),291(M+-OCH3,15), 273(M+-OCH3-H2O,12), 258,246,232, 222, 159, 145, 141, 128, 95, 87, 85, 74 (base peak, 100), 59. 1H NMRδ(CDCl3): 4.73(1H, dd, J= 4.0 Hz, J= 1.5Hz, C-1-H), 4.55(1H, d, J= 8.0Hz,C-1′-H), 3.79(1H, dd, J=3.0Hz, J= 3.0Hz, C-3′-H), 3.00(1H, dd, J= 9.0Hz,J= 9.0Hz, C-4-H), 2.22(1H, m, C-2-Ha), 1.60(1H, m, C-2-He), 1.33(3H, d,J= 6.0Hz,C-5-CH,), 1.31(3H,d,,J= 6.5Hz, C-5′-CH), 3.68(3H,s,,C-3′-OCH),3.31(3H,s,C-1-OCH). 13C NMR data were seen in Table 1. Ⅳ, tri-acetyl-α-methyl-dredehongbioside, colorless granular (from MeOH),mp. 135--137℃, [a]D22+ 88.2˚(c= 0.50, MeOH). MS(m/e, %): 488 (M+, 2), 388(M+-HOAc,2), 357(M+-OCH3-HOAc,33), 288, 187, 127, 116, 85, 74, 59, 43(basepeak, 100). 1H NMR,δ(CDCl3): 5.25(1H, ddd,.J= 11.0Hz, J=9.0Hz,.J= 5.5Hz,C-3-H), 4.86(1H, d, J= 8.0Hz, C-1′-H), 4.69 (1H, dd, J= 4.0Hz, J= 1.5Hz,C-1-H), 4.58(1H,m,C-2′-H),3.94(1H, dd, J= 3.0Hz,J= 3.0Hz,C-3′-H),3.64(1H,m,C-5-H), 3.22(1H,dd, J= 9.5Hz, J= 8.5Hz, C-4-H), 2.30(1H, m, C-2-Ha),1.67(1H,m,C-2-He), 1.31(3H, d, .J= 6.5Hz, C-5-CH3), 1.17(3H, d, J= 6.0Hz,C-5-CH3), 3.47(3H, s, C-3′-OCH3), 3.30(3H,s, C-1-OCH3), 2.10(6H, s, C-2′, C- 4′ -OCH3), 2.03(3H,s,C-3-OCH3).