(E)-脱氢二聚白藜芦醇-11,11′,13,13′-四甲醚的全合成

以3,5-二甲氧基苯甲酸(1)为起始原料, 经过甲醇酯化、氢化铝锂还原、四溴化碳溴代和Wittig-Horner反应,高产率的合成了Wittig-Horner试剂(5). 化合物5与对羟基苯甲醛(6)的羟基保护产物(7)偶联得到化合物(8),后者经去甲氧基亚甲基保护和仿生氧化偶联反应成功地全合成了(E)-脱氢二聚白藜芦醇-11,11′,13,13′-四甲醚(10). 通过1H NMR、13C NMR、IR、HRMS等测试技术确定化合物10为二聚芪类化合物(E)-脱氢二聚白藜芦醇-11,11′,13,13′-四甲醚,总收率48.93%.     

海洋真菌赤褐炭团菌FS521的次级代谢产物研究（英文）

从海洋真菌赤褐炭团菌(Hypoxylon rubiginosum) FS521中分离纯化得到17个聚酮类化合物,分别鉴定为4-乙酰氧基-8-甲氧基-3,4-二氢萘-1(2H)-酮(1)、4,8-二甲氧基-1-萘酚(2)、1'-羟基-4',8,8'-三甲氧基[2,2']联萘-1,4-二酮(3)、3,6-dimethyl-atromentin (4)、4-羟基-8-甲氧基-3,4-二氢萘-1(2H)-酮(5)、regiolone (6)、methylsclerone (7)、5-methylmellein(8)、3,5-二甲基-8-甲氧基-3,4-二羟基异香豆素(9)、9-甲氧基萘(10)、1,8-二甲氧基萘(11)、8-甲氧基-1-萘醇(12)、7-甲氧基-3-甲基异苯并呋喃(13)、3-甲基-4-羟基苯乙酸(14)、nodulisporipyrone A (15)、nodulisporipyrone B (16)、3,4-二甲氧基-乙酰苯乙醇(17).其中化合物1为新化合物,化合物2和3为新天然产物,新化合物的结构通过HRESIMS, 1D NMR和2DNMR等光谱技术确定.此外,对分离所得的化合物1～4进行了体外细胞毒活性测试,结果表明化合物3对SF-268、MCF-7、Hep G-2、A549有较强的细胞毒活性,其IC_(50)值分别为1.85、3.21、2.53、5.09mmol·L~(-1).     

从青藤碱制备具有(＋)-C-Normorphinan骨架的化合物

对青藤碱进行Mitsunobu甲基化反应, 得到O-甲基青藤碱(2); 2经过酸性水解、硼氢化还原以及高碘酸钠氧化开环得到O-甲基青藤碱二醛(5); 在哌啶存在下对5进行羟醛缩合反应, 区域选择性地闭环生成具有(＋)-C-normorphinan骨架的化合物(8S,12S,13R)-6,7-didehydro-3,4-dimethoxy-16-methyl-C-normorphinan-7-carboxaldehyde (7); 经过以上五步反应, 7的总收率约35%. 对7进行硼氢化还原得到化合物8; 化合物8以醋酐进行酯化得到化合物9. 化合物7以5% Pd/C为催化剂、1.01×105 Pa下与氢气作用发生双键氢化反应, 立体定向地得到化合物10, 从化合物10出发获得化合物11和12. 通过对化合物11的1H NMR, 13C NMR, 2D-NMR及NOESY等核磁共振分析确定化合物10, 11和12具有7S绝对构型.     

17-(2′,5′-二取代噁唑基)-雄甾-4,16-二烯-3-酮的合成及抗肿瘤活性研究

以4-雄烯二酮1为原料,用金催化甾炔法设计并合成了一系列17-(2′,5′-二取代噁唑基)-雄甾-4,16-二烯-3-酮衍生物4a~4k.所合成产物通过1H NMR,13C NMR,IR和HRMS方法进行了结构表征.以阿比特龙为阳性对照,通过3-(4,5-二甲基噻唑-2)-2,5-二苯基四氮唑溴盐(MTT)法测试了目标化合物对MCF-7(人乳腺癌细胞)、A549(人肺癌细胞)、Bel-7402(人肝癌细胞)、Hela(人宫颈癌细胞)和PC-3M-1E8(人前列腺癌细胞)的体外抗肿瘤活性.结果表明大多数化合物表现出了较好的抗肿瘤活性,其中化合物4c,4g,4i和4j的抗肿瘤活性与阳性对照物阿比特龙相当,且所测化合物对MCF-7有较好选择性作用,其IC50值在3.0~25.5μmol/L之间.     

新型两亲性氮杂六芳基苯的合成

以5-溴-2-十二烷基嘧啶为原料,经Sonogashira偶联等反应制得1,2-双(2-十二烷基嘧啶-5-基)乙炔(4); 1-溴-4-(2-(2-(2-甲氧基乙氧基)乙氧基)乙氧基)苯(5)与双频哪醇合二硼反应制得化合物(6); 4,4′-二溴苯偶酰与1,3-二苯基丙酮经羟醛缩合反应制得四芳基环戊二烯酮衍生物(7); 化合物4与7经Diels-Alder反应制得化合物8; 8与6〖STBZ〗通过Suzuki-Miyaura偶联反应合成新型两亲性氮杂六芳基苯(9),化合物6~9为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS(MALDI-TOF)表征。     

多取代香豆素类化合物的合成及抗真菌活性

以前期合成的6/7/8-羟基-3-香豆素甲酸乙酯为原料,使其与卤代烃发生Williamson反应制得化合物1～6;以2,4-二羟基苯甲醛为原料,使其与季鏻盐发生Wittig反应得到中间体化合物7;以取代间苯二酚为原料,使其与乙酰乙酸乙酯发生Pechmann缩合得到化合物8～10;在TBAB催化下,化合物7～10与相应的卤代烃发生Williamson反应制得化合物11～17;通过~1H NMR、~(13)C NMR和ESI-MS等波谱技术确定了所有目标化合物的结构。在50μg·mL~(-1)时,以醚菌酯或多菌灵为阳性对照,测定了所有化合物对12种常见植物病原真菌的抑制作用,发现它们均具有不同程度的抗菌活性。其中,4、5、7和13对苹果腐烂菌、苹果炭疽菌、白菜黑斑、水稻稻瘟、烟草赤星、苹果轮纹等6种植物病原菌的抑制活性高于阳性对照醚菌酯或多菌灵。由此可见,化合物4、5、7和13具有开发成新型农用抗菌剂的潜力,这为后续香豆素类抗菌剂的研发奠定了理论基础。     

6-位修饰的吉非替尼衍生物合成及细胞毒活性研究

以2-氨基-4,5-二甲氧基苯甲酸为起始原料,经关环,选择性脱甲基,醋酸酐保护,氯代,与3-氯-4-氟苯胺取代,去保护得到关键中间体4-(3-氯-4-氟苯胺)-7-甲氧基-喹唑啉-6-醇.再经过6-位羟基成醚、成酯反应合成了共计23个吉非替尼衍生物.所有目标化合物通过IR,1H NMR,13C NMR,HRMS等结构确证.并采用四甲基偶氮唑盐(MTT)法对所得目标化合物进行了细胞毒活性测试,结果发现部分化合物具有一定的抑制活性,其中化合物7b,7c,7d,8a,8m抑制人非小细胞肺癌细胞(A549)增殖活性和化合物7c,8m抑制人肝癌细胞(Hep G-2)增殖活性与吉非替尼相当.     

中国南海软珊瑚Scleronephthya sp.化学成分的研究

对中国南海的软珊瑚Scleronephthya sp.的化学成分进行研究,从有免疫调节活性的乙醚可溶物中分离鉴定了13个化合物,经1H NMR,13C NMR,HMQC,HMBC,1H-1H COSY和MS等光谱分析并结合文献数据,确证其结构分别为:3β-羟基-20-烯孕甾烷乙酸酯(1),3β-羟基-5,20-二烯孕甾烷乙酸酯(2),3-酮-20-烯孕甾烷(3),1,2-环氧-3-酮-20-烯孕甾烷(4),1,20-二烯-3-酮孕甾烷(5),1-烯-3-酮-20S-甲基-21-羟基孕甾烷乙酸酯(6),1-烯-3-酮-20β-羟基孕甾烷乙酸酯(7),1-烯-3,22-二酮胆甾烷(8),1,24-二烯-3-酮-22,23-二羟基胆甾烷(9),O-methylisogrifolin(10),(1R,3S,4S,7E,11E)-3α,4α-环氧-7,11,15-三烯西松烷(11),玉米黄素12和6-溴-3-羧酸吲哚(13),其中化合物4,6和10是首次从自然界分离得到.首次对化合物6,7和10的波谱数据进行了报道,而且利用2D NMR对其进行了全归属.对化合物1～7可能的生源关系也进行了探讨.化合物6和7对人宫颈癌细胞(HELA)有抑制活性,IC50分别为3.3和6.3 mol/L;化合物7对肝癌细胞(BE7402)和人白血病细胞(HL-60)也显示抑制活性,IC50分别为3.1和0.26mol/L;化合物11对COX-2显示强烈的抑制活性,IC50为0.455 mol/L.     

南鹤虱中两个新的倍半萜类化合物（英文）

从中药南鹤虱(Fructus carotae)中分离纯化得到7个倍半萜类化合物,分别鉴定为7-ethoxy-4(15)-oppositen-1β-ol(1),11-乙酰氧基-8β-当归酰氧基-15-甲氧基-4α,5α-环氧愈创木烷-3-酮(2),11-乙酰氧基-8β-丙酰氧基-4-愈创木烯-3-酮(3),1-oxo-5α,7αH-eudesma-3-en-15-al(4),1β-hydroxy-4(15),7-eudesmadiene(5),1β-hydroxy-4(15),5E,10(14)-germacratriene(6),1β-hydroxy-4(15),5-eudesmadiene(7).其中化合物1和2为新的化合物,新化合物的结构进一步通过HR-ESIMS,1D NMR和2D NMR等光谱技术确定.     

Methyl-5β-hydroxy-4-oxo-11(13)-dehydroiphionoate的立体选择性全合成

Methyl-5β-hydroxy-4-oxo-11(13)-dehydroiphionoate(10)和其生源前体Methyl-4,5-dioxo-seco-isocostoate(9)是从生长于非洲南部和东部的熊菊属植物U.eckloniana中分离出的两种桉烷衍生天然产物,具有一定的生理活性[1].我们以(+)-二氢香芹酮(1)为起始原料,通过十步反应,进行了这两个化合物的不对称全合成工作,成功地得到了化合物8,化合物9和10的合成工作正在进行中.所有化合物均经1H NMR,13C NMR,IR,MS等光谱数据确证.     

Synthesis and characterization of cyano-substituted carborane-based compounds. Molecular structure of [1-(4-C7H7)-12-(C5H3-3-(CN)-3,4-(CH3)2)-C2B10H10

The reaction of cyanogen chloride with [1-(4-C(7)H(7))-12-(C(5)H(3)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (7) was found to yield two new C(5)-substituted carborane cluster-based compounds, [1-(4-C(7)H(7))-12-(C(5)H(2)-3-(CN)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (8) and [1-(4-C(7)H(7))-12-(C(5)H-2,4-(CN)(2)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (9). This cyano-substitution pattern is in contrast to the known substitution for the analogous organic quinarene[5.6.7] system. The observed unique cluster-based products may be understood by a combination of steric and electronic effects. Compounds 8 and 9 were characterized by complete multinuclear NMR, (1)H-(1)H COSY NMR, (1)H-(13)C HMQC NMR, FTIR, UV-Vis, IR, MS data and a single crystal analysis for 8 [X-ray data for 8: C(17)H(25)B(10)N, monoclinic, space group P2(1)/n with cell constants a = 8.6794(17) ?, b = 11.021(2) ?, c = 43.175(9) ?, β = 91.00(3)°, V = 4129.2(14) ?(3), Z = 8, R(1) = 0.0729, wR(2) = 0.1464].     

Inclusion complexation of diquat and paraquat by the hosts cucurbit[7]uril and cucurbit[8]uril

The binding interactions in aqueous solution between the dicationic guest diquat (DQ(2+)) and the cucurbit[7]uril (CB7) and cucurbit[8]uril (CB8) hosts were investigated by (1)H NMR, UV/Vis, and fluorescence spectroscopy; mass spectrometry; single-crystal X-ray diffraction; and electrochemical techniques. The binding data were compared with previously reported results for the related paraquat guest (PQ(2+)). DQ(2+) was found to bind poorly (K=350 m(-1)) inside CB7 and more effectively (K=4.8 x 10(4) m(-1)) inside CB8. One-electron reduction led to increased binding affinity with both hosts (K(r)=1 x 10(4) m(-1) with CB7 and K(r)=6 x 10(5) m(-1) for CB8). While (1)H NMR spectroscopic data revealed that DQ(2+) is not fully included by CB7, the crystal structure of the CB8DQ(2+) complex-obtained from single-crystal X-ray diffraction-clearly establishes its inclusion nature. Overall, both diquat and its one-electron reduced radical cation are bound more effectively by CB8 than by CB7. In contrast to this, paraquat exhibits selectivity for CB7, but its radical cation forms a highly stable dimer inside CB8. These differences highlight the pronounced sensitivity of cucurbit[n]uril hosts to guest features such as charge, charge distribution and shape.     

Two New Eremophilenolides from Ligularia sagitta

Chemical investigation of L.sagitta afforded two new eremophilenolides, which were identified as 6β-angeloyloxy-10β-hydroxy-8 β-methoxy-eremophil-7(11)-en-12, 8α-olide (1) and 6β, 8β-dimethoxy-10β-hydroxy-eremophil-7(11)-en-12, 8α-olide (2). Their structures were estab- lished by spectroscopic methods including 2D NMR experiments.     

95Mo and 17O NMR studies of aqueous molybdate solutions

Aqueous molybdate solutions with molybdenum concentrations of [Mo]=1, 0.4, and 0.2 M have been studied by NMR at pH 7-1 and in 0.3-6 M HClO4. The 95Mo NMR spectrum of isopolyanion (IPA) Mo7O24(6-) (I) at pH=5 consists of a signal at 210 ppm and two overlapping peaks at 32 and approximately 15 ppm with the intensity ratio approximately 1:4:2, and that of beta-Mo8O26(4-) (II) consists of two signals at approximately 100 and 10 ppm with the intensity ratio approximately 1:3. A broad 95Mo NMR line at around 0 ppm was observed in the pH range of IPA Mo36O112(8-) (III), and a signal of cationic oxospecies including MoO2(2+) (IV) was observed from -62 to -69 ppm. Two protonation sites of IPA I have been identified from 17O NMR spectra, which suggests binding of up to two protons. The distribution diagram, derived from the 95Mo NMR spectra, is given for [Mo]=0.4 M. The 95Mo NMR signals shift to lower frequencies with increasing number and strength of the Mo-O terminal bonds.     

Two new eremophilanolides from Xanthium sibiricum

Two new eremophilanolides, sibiriolides A (1) and B (2), were isolated from the aerial parts of Xanthium sibiricum. The structures of the new compounds were identified as 4S,5R,7R,8R, 11R-2-oxo-1(10)-eremophilen-12,8-olide (1) and 4S,5R,7R,8R,11S-2-oxo-1(10)-eremophilen-12,8-olide (2) by HREIMS and NMR spectroscopic techniques in combination with X-ray crystallographic analysis and CD measurements.     

Contribution of the nido-[7,8-C2B9H10]- anion to the chemical stability, basicity, and 31P NMR chemical shift in nido-o-carboranylmonophosphines

The icosahedral dicarboranes and their decapitated anion, 1-R'-1,2-C(2)B(10)H(10) (closo) and [7-R'-7,8-C(2)B(9)H(10)](-) (nido), exert a distict influence at the alpha position of substituents attached to the cage carbon atom. The closo fragment is electron-withdrawing while the nido anion is electron-releasing. These effects are studied by (31)P NMR, phosphorus oxidation, and phosphorus protonation in [7-PR(2)-8-R'-7,8-C(2)B(9)H(10)](-) species. The (31)P NMR chemical shift dependence is related to the R alkyl or aryl nature of [7-PR(2)-8-R'-7,8-C(2)B(9)H(10)](-). No direct relationship to the nature of the R substituent on the nido-carboranylmonphosphine toward oxidation has been found. The basicity of the nido-alkylcarboranylmonophosphines is the highest while the lowest corresponds to the nido-arylcarboranylmonophosphines. Interpretation can be carried out qualitatively by considering the electronic properties of the cluster and the nature of the R groups. The influence of R' is less relevant. Confirmation of the molecular structure of the oxidated and protonated nido-carboranylmonophosphine compounds was obtained by X-ray diffraction analysis of [NBu(4)][7-P(O)Ph(2)-8-Ph-7,8-C(2)B(9)H(10)] and [7-PH((i)Pr)(2)-8-Me-7,8-C(2)B(9)H(10)].     

Syntheses, Crystal Structures and NMR of Two Molybdenum Complexes with 2,3-Dihydroxynaphthalene

Two complexes [H3N(CH2)2NH2]2[MoO2(C10H8O2)2] (1) and (C7H10N2)2- [MoO2(C10H8O2)2] (2) were obtained at nearly the same reaction condition and characterized by IR, 1H and 13C NMR and single-crystal X-ray diffraction. Both of the complexes possess complex anion [MoO2(C10H8O2)2]2- which shows a pseudo-octahedrally coordinated fashion. In complex 1, ethyldiamine presents just as a cation. However, in complex 2, ethyldiamine combines with the acetyl acetone as a byproduct which is confirmed by NMR.     

Microbial hydroxylation of S-(-)-perillyl alcohol by Fusarium heterosporium

S-(-)-Perillyl alcohol (p-mentha-1, 8-diene-7-ol) (1) (500 mg) was converted by Fusarium heterosporium ATCC 15625 over 10 days at 25 degrees C to a new metabolite, 1,2-dihydroxyperillyl alcohol (p-mentha-8-en-1,2,7-triol) (3) in a yield of 13% (70 mg). The structure of 3 was established by IR and NMR spectroscopic, specific rotation, and mass spectral studies.     

A new eremophilane-type sesquiterpene from Ligularia virgaurea

A new eremophilane-type sesquiterpene,1α,8β,10β-trihydroxy-6β-(2-methylacryloyl)oxyeremophil-7(11)-en-8α,12-olide, was isolated from the roots of Ligularia virgaurea.Its structure was established on the basis of various spectroscopic analyses, including the 1D,2D NMR techniques and HR-ESI-MS.