1.
Syntheses of enantio-enriched chiral building blocks from L-glutamic acid - 黃培强
Starting from lactone-amide 8, easily derived from L-glutamic acid, enantioselective syntheses of (S)-tetrahydrofuran 2-carboxamide derivative 2 and a protected (S)-3-hydroxypiperidin-2-one (3) are reported. The building block 3 was converted to (2S,3R)-3-hydroxypipecolamide (6) by a three-step procedure. A solvent altered H-bonding capacity leading to a highly chemoselective tosylation of the primary hydroxyl group in the presence of an alpha-hydroxy-carboxamide was observed.
10.
1,1’-联萘-2,2’-二酚及其孟基碳酸酯衍生物的手性高效液相色谱 - 阮源萍; 敖小平; 陈安齐; 黄培强; 靳立人
用高效液相色谱法考察了 1,1’ 联萘 2 ,2’ 二酚及其单和双氯代孟基碳酸衍生物等三对手性化合物在 (S) 特 亮氨酸基 (S) 1 (α 萘基 )乙胺脲型手性色谱柱上的拆分行为 .讨论了三元流动相中 1,2 二氯乙烷和乙醇含量的变化以及不同极性调节剂对分离的影响 ,探讨了这些手性化合物在脲型手性固定相上的可能拆分机理 .该法已用于 ( ) 孟基氯代碳酸酯化学拆分外消旋 1,1’ 联萘 2 ,2’ 二酚过程相关产物的光学纯度测定.
The chiral resolution of 1 ,1’2binaphthalene22 ,2’2diol (1) , 1 ,1’2binaphthalene22 ,2’2diol2mono2[ (2)2men2
thyl ] carbonate (2) and 1 ,1’2binaphthalene22 ,2’2diol2bi2[ (2)2menthyl ] carbonate (3) was studied by high performance
liquid chromatography using (S)2tert2leucine and (S)212α2NEA as chiral stationary phase. The effect of different content of
1 ,22dichloroethane and ethane , as well as a different polar modifier in mobile phase on the chiral separation was discussed.
A baseline separation of optical isomers of compounds 1 and 2...
11.
含有机配体的活性双过氧钒配合物与组氨酸的相互作用研究 - 周兴旺; 叶剑良; 陈忠; 陈志伟; 黄培强
在合成和表征了 4种具有较强生物活性双过氧钒配合物K3 [VO(O2 ) 2 (ox) ]·2H2 O ,Na[VO(O2 ) 2 (bipy) ]·5H2 O ,K[VO(O2 ) 2 (phen) ]·3H2 O和K2 [VO(O2 ) 2 (pic) ]·2H2 O [分别缩写为pV(ox) ,pV(bipy) ,pV(phen)和pV(pic) ,其中ox为草酸根 ,bipy为 2 ,2′ 联吡啶 ,phen为邻菲咯啉 ,pic为 2 羧酸吡啶负离子 ]的基础上 ,利用多种NMR技术和电喷雾质谱 (ESI MS)研究了这 4种含有机配体双过氧钒配合物与组氨酸 (His)在溶液中的相互作用以及反应物浓度、时间、pH等对相互作用体系的影响 .51VNMR跟踪监测的结果表明 :双过氧钒配合物pV(ox)和pV(pic)与His在中性水溶液中存在强配位相互作用 ,而pV(bipy)和pV(phen)与His在中性水溶液中无明显作用 .我们还利用谱学方法确定了pV(ox)和His相互作用后所生成产物是pV(ox)分别与His咪唑基上的 3 N和 1 N配位的一对异构体.
In order to explore the structure2activity relationship and molecular mechanism of the specific
recognition between peroxovanadium (pV) complexes bearing organic ligands and the target enzymes of tyrosine
phosphatase , several NMR techniques and ESI2MS were used to study the interactions of four pV complexes
{pV(ox) , pV ( bipy) , pV (phen)...
12.
[VS_4-Cu_n](n=3-6)簇合物成簇反应的~(51)V NMR研究 - 叶剑良; 郑发鲲; 陈忠; 谢鸿琛; 陈志伟; 黄培强
在核磁管内模拟反应体系 (NH4)3VS4/Et4NBr/CuBr/PPh3在CH2 Cl2 溶液中生成[VS4 Cun](n =3 6 )簇合物的过程 .利用 51 VNMR技术对反应过程进行准原位的实时监测 ,研究 [VS4 Cun](n =3 6 )簇合物的成簇条件和机理以及配体对成簇过程的影响 .本文还详细讨论了反应溶液中不同浓度的PPh3对 [VS4 Cu4]簇合物的51 VNMR化学位移的影响 .
The reaction system (NH4 ) 3VS4/ Et4NBr/ CuBr/ PPh3 in CH2Cl2 for self2assembling of [VS 4-Cu n ] ( n from 3 to 6)clusters was simulated in NMR tube. After the relationship between the 51V NMR chemical shift s and the number of copper atoms in this family cluster was established theoretically and experimentally , 51V NMR was used as a pseudo in sit u and real2time method to monitor and identify possible product s during the reaction process....
13.
衍生化高效液相色谱法拆分1,1′-联萘-2,2′-二酚光学异构体 - 阮源萍; 敖小平; 陈安齐; 黄培强
以基碳酸酰氯作衍生化试剂 ,采用高效液相色谱拆分 1,1′ 联萘 2 ,2′ 二酚光学异构体。当采用LichrosorbSi 6 0 (4mm× 30 0mm ,5 μm)柱 ,紫外 2 75nm检测 ,正己烷 乙醇 (98.5 1.5 ,V V)为流动相 ,1,1′ 联萘 2 ,2′ 二酚单基碳酸酯的分离因子和分离度分别为 1.36 8、3.0 5 1;用正己烷 乙醚 (98.5 1.5 ,V V)为流动相 ,1,1′ 联萘 2 ,2′ 二酚双基碳酸酯的分离因子和分离度分别为 1.0 5 5、1.347。这一方法可简便、快速地测定联萘二酚单基碳酸酯拆分样品的光学纯度.
1 ,1′2Binaphthalene22 ,2′2diol2mono2[ (2)2menthyl ] carbonate (3) and 1 ,1′2binaphthalene22 ,2′2diol2
bis2[ (2)2menthyl ] carbonate (4) are intermediates in the chemical resolution of racemic 1 ,1′2binaphthalene22 ,2′2
diols (1) utilizing (2)2( 1R)2menthyl chloroformate ( 2) as the derivating agent . In this paper , the optical
separation of compound (3) and (4) has been investigated by high performance liquid...
15.
1,1’-联萘-2,2’-二酚-单-[(-)-孟基]碳酸酯旋光异构体的反相高效液相色谱分离及光学纯度测定 - 阮源萍; 陈安齐; 刘文远; 郑锦丽; 黄培强
采用反相高效液相色谱法分离了 1 ,1’-联萘 - 2 ,2’-二酚 -单 [(- ) -孟基 ]碳酸酯旋光异构体 .考察了这一对旋光化合物的反相高效液相色谱行为 .结果表明 ,C1 8及 C8柱和醇 /水流动相体系适合于这一对旋光异构体的分离 .进一步优化了色谱分离条件 ,并用于它们的光学纯度测定。
R)1,1’inaphthalene2,2’diolmono[()menthyl] carbonate and (S)1,1’binaphthalene2,2’diolmono[()menthyl] carbonate were separated by reversephase high performance liquid chromatography . The effects of different types of stationary phase and mobile phase composition on the optical isomeric separation were investigated. The result showed that the C 18 or C 8 column and alcoholwater as mobile phase are suitable for the separation. The mechanism of separation is also discussed.
17.
活性过氧钒配合物对酪氨酸磷酸酶的抑制作用 - 周兴旺; 陈忠; 陈清西; 叶剑良; 黄培强; 吴钦义
为研究过氧钒配合物降血糖作用的构效关系规律和构效关系的分子机制 ,从牛心分离纯化了电泳纯的低分子量牛心酪氨酸磷酸酶 (BHPTPase)。合成并用51VNMR和13CNMR以及IR等谱学表征了 4种具有很强生物活性的过氧钒配合物K3[VO(O2 ) 2 (ox) ]·2H2 O、Na[VO(O2 ) 2 (bipy) ]·5H2 O、K[VO(O2 ) 2 ( phen) ]·3H2 O和K2 [VO(O2 ) 2 ( pic) ]·2H2 O。4种配合物对BHPTPase都有极显著的抑制作用 ,抑制强度的IC50 分别为 0 .2 2、0 .3 6、0 .90和0 .2 8μmol/L ,并根据实验结果讨论了过氧钒配合物的氧化能力和有机配体的空间位阻对构效关系的影响。 In order to study the st ructure2activity relationship and molecular mechanism of insulin2mimetic
peroxovanadium complexes , the low2molecular2weight BHPTPase f rom bovine heart has been purified mainly by
chromatography of DEAE2cellulose and Sephadex G275 , which was showed homogenicity on SDS2PAGE. Four
bioactive peroxovanadium(pV) complexes bpV(ox) , bpV(bipy) , bpV(phen) and bpV(pic) , [VO(O2) 2L ] n - ,
where L = oxalic acid dianion(ox) , bipyridine...
18.
D - Quinic Acid, A Versatile Chiron in Organic Synthesis - 黄培强
综述了D-奎尼酸在各种环状和链状生物活性化合物合成中的应用。奎尼酸分子中特有的顺式γ-羟基羧酸的结构单元提供了区别分子中各种羟基,以及进行其它区域选择性和立体选择性控制的方便途经。奎尼酸的结构特征以及其价廉、易得的优点,使之成为一个有用的而且重要的手性合成子。This review describes the use of D - Quinic acid in the synthesis of various natural or un -natural bioactive compounds. Because of the presence of cis - r - hydroxyl - carboxyl subunit in quinic acid, a lactone ring can be formed easily. The thus formed rigid system provides good control elements for many regie - and stereoselective transformations. Besides, D - quinic acid is also readily available. These make this compound a useful and versatile chiron for both cyclic (hexanoids and pentanoids) and acyclic bioactive compounds.
1.
