4,5-二苯基-2-取代基-1-磺酰基咪唑的合成

用多种磺酰氯或磺酸酐与4,5-二苯基-2-取代-1-磺酰基咪唑负离子反应, 合成了10个未见文献报道的1-磺酰基咪唑类化合物. 所有化合物均经1H NMR和13C NMR确证.     

三乙胺促进的α-卤代酮C—C键断裂:合成α-乙酰氧基芳基酮（英文）

C—C键断裂在有机合成中有着重要的作用.报道了一种胺促进的α-卤代酮化合物C—C键断裂的新方法,该方法无需使用过渡金属催化剂以及氧化剂.采用这种方法以廉价的α-卤代酮化合物制备了多种α-乙酰氧基芳基酮化合物.     

Pd/C催化氧气对1,3-二羰基化合物的α-位氧化

以碳酸钾作碱,DMF作溶剂,5%Pd/C催化1,3-二羰基化合物在室温下与氧气反应,直接得到α-羟基化合物,其结构经NMR和MS表征.     

4-(对取代苯基)-2-[2-(取代苯基)呋喃-4-甲酰胺]-1',3',4'-均三唑[1,2-d]-1,3,4-噻二唑类衍生物的合成和生物活性

以1-氨基-5-巯基-2-(对取代苯基)-1,3,4-均三唑和5-取代苯基-2-呋喃甲酰异硫氰酸酯为原料, 合成了10个未见文献报道的含苯环连呋喃的均三唑并噻二唑类衍生物, 通过元素分析, ¹H NMR, IR和MS确定化合物的结构, 初步生物活性测试表明标题化合物具有一定的除草活性.     

微波作用下1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑的合成及生物活性

采用微波和相转移催化法通过1-苯基-5-(4-苯基-1,2,4-三唑-5-巯基-3-甲硫基)四唑(2)与2-氯乙酰芳胺(3)反应高效、快速地合成了10种尚未见文献报道的1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑. 其结构经 IR, ¹H NMR, ¹³C NMR 和元素分析表征. 生物活性实验结果表明, 该类化合物在较低浓度下部分化合物对小麦芽有很好的促进作用.     

铑催化3-重氮吲哚-2-亚胺与吡唑啉酮的C—H官能团化反应制备3-吡唑基吲哚（英文）

报道了一种在Rh2(OAc)4存在下α-亚胺卡宾和吡唑啉酮的高效C—H官能团化反应.该方法通过C—C键的形成为构建结构多样的3-吡唑基吲哚化合物提供了一种快速、直接的途径,反应具有中等至优异的产率和良好的官能团耐受性.     

1-对甲苯基-5-取代苯基亚胺基-1,2,3-三唑甲酸/甲酰胺的合成及生物活性研究

以对甲基苯胺为原料,经过重氮化反应生成对甲基叠氮苯(1).在强碱性条件下,1分别与氰基乙酸乙酯、氰基乙酰胺反应,制得中间体1-对甲苯基-5-氨基-1,2,3-三唑甲酸乙酯(2)和1-对甲苯基-5-氨基-1,2,3-三唑甲酰胺(5);中间体2经水解生成1-对甲苯基-5-氨基-1,2,3-三唑甲酸(3),进而在弱酸性条件下与取代苯甲醛反应得到6个未见文献报道的目标化合物1-对甲苯基-5-取代苯基亚胺基-1,2,3-三唑甲酸(4a～4f),5与取代苯甲醛反应得到6个未见文献报道的目标化合物1-对甲苯基-5-取代苯基亚胺基-1,2,3-三唑甲酰胺(6a～6f),化合物的结构均经IR,1H NMR,13C NMR确证.初步生物测试表明,12个化合物均表现出良好的抑菌活性,其中化合物4d～4f和6d～6f对金黄色葡萄球菌、白色念球菌的最小抑菌浓度(MIC)值为2～8μg/mL,抗菌效果优于氟康唑和三氯生.     

1,5-二取代吡唑基-1,4-戊二烯-3-酮类化合物的合成及生物活性研究

设计合成了13个未见文献报道的1,5-二取代吡唑基-1,4-戊二烯-3-酮类化合物, 其结构经元素分析, 1H NMR, IR确证. 初步生物活性测试结果表明, 部分化合物有一定的抗烟草花叶病毒(TMV)活性, 所有化合物抑菌活性较低.     

4-[3-(4-溴苯基)-3-氧代-1-芳基丙氨基]-N-(嘧啶-2-基)苯磺酰胺的合成及其α-葡萄糖苷酶抑制活性初步研究

为了寻求新颖的抗糖尿病药物, 我们将芳香醛、对溴苯乙酮和磺胺嘧啶通过一步反应直接合成了16个未见报道的含有磺胺嘧啶结构的β-氨基酮化合物, 制备方法简便、反应条件温和, 收率为10.0%～80.1%. 所制备的化合物通过1H NMR, 13C NMR, MS和HRMS进行结构表征与确证. 对这些化合物进行α-葡萄糖苷酶抑制活性初步检测, 结果表明部分化合物在低浓度范围(8.1～9.3 nmol•mL－1)具有一定的α-葡萄糖苷酶抑制活性.     

9-乙酰氧基乙基-6-烷氨基-2-烷硫基嘌呤的合成及抗血小板凝集活性评估

以2-氨基-6-氯嘌呤(1)为原料,与2-溴乙基乙酸酯反应得到9-乙酰氧基乙基-2-氨基-6-氯嘌呤(2);2经重氮-烷硫化得到9-乙酰氧基乙基-2-烷硫基-6-氯嘌呤(3);3经胺解反应得到14个未见报道的9-乙酰氧基乙基-6-烷氨基-2-烷硫基嘌呤化合物4.这些化合物的结构经IR,1H NMR,13C NMR及HRMS得到表征,同时进行了抗血小板凝集活性测试.     

278.15-313.15 K下糖-水二元体系的介电常数

测定了D-(-)-果糖、D-(+)-葡萄糖、D-(+)-半乳糖、D-(+)-木糖和D-(-)-核糖五种糖的水溶液在不同质量摩尔浓度和不同温度下的介电常数(D). 结果表明, 在一定温度下, 这些糖的水溶液介电常数对数值都随糖浓度的增大而减小; 在一定糖浓度时, 介电常数值随温度升高而减小. 果糖、葡萄糖、半乳糖和木糖水溶液的介电常数(D)随温度的变化均满足关系式: lgD=A1-B1(T-298.15), 而核糖水溶液则符合: lgD=A2-B2(T-298.15)+C2(T-298.15)2. 此外, 这五种糖的水溶液的介电常数与摩尔分数(x)满足关系式: lg(D/D0)=-B3x. 在相同温度和浓度时, 介电常数的大小顺序通常为: 水>半乳糖-水>果糖-水>葡萄糖-水≥木糖-水(而核糖较特殊).     

Synthesis of diastereomeric,deoxy and ring-expanded sulfone analogues of aigialomycin D

Several analogues of the fungal natural product aigialomycin D (AmD) have been synthesised. These include the stereoisomer 5′R,6′S-AmD, 2,4-di-deoxyAmD, 1′,2′,7′,8′-tetrahydroAmD and a 15-membered macrocyclic sulfone. Growth inhibitory activities of these compounds against the HL-60 leukaemic cell line were measured. The ring-expanded sulfone and tetrahydro-analogue were found to have similar IC₅₀ values to the natural product, whereas the 5′R,6′S-stereoisomer was inactive. Energy minimisation of AmD and the synthesised analogues resulted in a range of lowest energy conformers, from planar, open arrangements of the macrocycle in AmD and tetrahydroAmD to bent, L-shaped structures for the sulfone. The synthesis of methyl orsellinate was investigated and optimised as part of this work. A stereodivergent route to both enantiomers of the diol fragment from d-ribose was also achieved.     

Enantioselective total synthesis of aigialomycin D

An efficient, convergent approach for the total synthesis of aigialomycin D 1 is described. Key features of the synthetic strategy include (a) a Sharpless asymmetric epoxidation reaction and selective opening of a 2,3-epoxy alcohol to elaborate the two hydroxy-bearing stereogenic centers at the C5′ and C6′ positions; (b) a Kocienski modified Julia protocol to construct the two E-configured double bonds; and (c) Yamaguchi macrolactonization to acccess the 14-membered macrocyclic ring.     

Carboalumination-Epoxide Ring Opening for the Formation of 1,4-Disubstituted (Z)-3,6-Alkadienols

Allylalumination of alkynes (i.e. forming Negishi's (Z)‐alkenyl dialkylalane) followed by alkenylation of epoxides provides 1,4‐disubstituted (Z)‐3,6‐alkadienols. The alkenylation can be facilitated by the presence of a neighbouring coordinating group in the epoxides. This "one‐pot" approach has been successfully applied in the large‐scale production of C10–C15 fragment of 9,10‐didehydroepothilone D (a synthetic epothilone analog as an anti‐cancer agent in phase 2 clinical trials).     

Asymmetric Total Synthesis of the Complex Polycyclic Xanthone FD‐594

A highly convergent approach was developed to achieve the first asymmetric and scalable total synthesis of FD‐594, a complex polycyclic xanthone natural product from Streptomyces sp. TA‐0256, in a longest linear sequence (LLS) of 20 steps. The trans‐9,10‐dihydrophenanthrene‐9,10‐diol fragment (B‐C‐D ring) was generated through a new strategy involving asymmetric dihydroxylation followed by Cu‐mediated oxidative cyclization. Late‐stage stereoselective glycosylation assembled the angular hexacyclic framework with a β‐linked 2,6‐dideoxy trisaccharide fragment.     

PLGA-(L-Asp-alt-diol)(x)-PLGAs with different contents of pendant amino groups: synthesis and characterization

A series of novel biodegradable multi-block copolymers PLGA-(L-Asp-alt-diol)(x)-PLGA with pendant amino groups was synthesized by ring-opening polymerization of D,L-lactide/glycolide(D,L-LA/GA) (75/25) using poly(N-Cbz-L-Asp-alt-diol)s as macroinitiator and stannous octoate as catalyst, in which the N-Cbz-L-Asp represents N-carbobenzyloxy-L-aspartic acid and diols are ethylene glycol, triethylene glycol, PEG200, and PEG600, respectively. Their structures and properties were characterized by FTIR, (1)H NMR, DSC, GPC, and elemental analysis (EA). The contents of the L-Asp unit in the copolymers were increased from 12.9 to 79.3 mmol.g(-1) with decreasing the chain length of the diol, while the glass transition temperatures of the copolymers were decreased from 27.1 to 11.7 degrees C with increasing the chain length of the diol. Thus, the results in this study provide a way to prepare biomaterials with different L-Asp unit densities or different number of bioactive sites as well as different properties through adjusting the chain length of the diol. Synthesis of PLGA-(N-Cbz-L-Asp-alt-diol)(x)-PLGA copolymers.     

异核苷低聚核苷酸的合成及其酶促稳定性

用磷酸三酯法在溶液中合成了两个带有３′－（Ｓ）－胸腺嘧啶基－４′－（Ｒ）－羟基－５′－（Ｓ）－羟甲基四氢呋喃的三脱氧核苷酸３和４。与三脱氧核苷酸（２）相比，化合物３和４对核酸酶Ｓ１具有更大的稳定性。     

Aigialomycins A-E, new resorcylic macrolides from the marine mangrove fungus Aigialus parvus

Aigialomycins A-E (2-6), new 14-membered resorcylic macrolides, were isolated together with a known hypothemycin (1) from the mangrove fungus, Aigialus parvus BCC 5311. Structures of these compounds, including absolute configuration, were elucidated by spectroscopic methods, chemical conversions, and X-ray crystallographic analysis. Hypothemycin and aigialomycin D (5) exhibited in vitro antimalarial activity with IC(50) values of 2.2 and 6.6 microg/mL, respectively, while other analogues were inactive. Cytotoxicities of these compounds were also evaluated.     

A Density Functional Study on the Geometries of Compounds Fe(HCN)n+(n = 1～6)

The possible geometries of Fe(HCN)n+ (n = 1～6) compounds were studied by using DFT/UB3LYP/6-31G(2df) method. The structure and ground state of each fragmental ion are C∞v (4∑+ or 6∑+), D∞h(4∑g+), D3h (4A1'), C2v or Td or C3v (4A1), and D3h (4A1') or C4v( (2A1') sequentially with n = 1～5. For the compound Fe(HCN)6+, the possible geometry was not obtained. The sequential incremental interaction energy (-△(△E)), dissociation energy (△D0), enthalpy (-△(△H)) and Gibbs free energy (-△(△G)), and frequencies for HCN-Fe(HCN)n-1+ were also calculated, and the results are all in good agreement with the experiments. The bond length of Fe-N is lengthened with the increase of cluster size, and the strength of Fe+-N coordination bond varies nonmon- tonically as increasing the number of ligands. The Fe+-N bond of Fe(HCN)2+ is the strongest in all compounds.     

核磁共振方法表征2,2''''-二(对羧酸苯氧基)-1,1''''联萘

利用１Ｈ ＮＭＲ，１３Ｃ ＮＭＲ研究了 ２，２’－二（对羧酸苯氧基）－１，１’－联萘结构，并通过１Ｈ－１Ｈ ＣＯＳＹ及１３Ｃ－１Ｈ异核相关谱进一步确定了其１Ｈ谱和１３Ｃ谱中各谱峰的归属，为同类化合物的表征提供了一个依据。