手性螺环/环丙烷类衍生物的合成及晶体结构研究

利用5-(l-孟氧基)-3-溴-2(5H)-呋喃酮新手性源合成子1与亲核试剂乙醇发生串联的不对称双Michael加成/分子内亲核取代反应,合成了用一般方法难以得到的含有多个手性中心的螺[1-溴4-l-孟氧基-5-氧杂-6-氧代双环[3.1.0]己烷-2,3'-(4'-乙氧基-5'-孟氧基丁内酯)]4.详细报道了4的两种合成方法和结构分析数据.经X射线四圆衍射确定了4分子的立体化学结构和绝对构型.此结果为研究某些生物活性分子提供了有价值的合成途径.     

手性2，5－双口恶唑啉噻吩的合成及应用研究

手性２，５－双口恶唑啉噻吩的合成及应用研究许遵乐蔡敏汪波刘汉标（中山大学化学系，广州５１０２７５）关键词２，５－双口恶唑啉噻吩，Ｃ－２对称手性试剂，ＮＭＲ位移试剂，１，１′－联－２－萘酚，对映体分类号Ｏ６２６．１２具有Ｃ－２对称因素的手性双口恶唑啉...     

手性金属试剂催化的不对称合成及其工业应用

研究报告了不同类型的不对称催化反应,介绍了它们在医药、农药、香精、食品添加剂等方面的实际应用。     

2-［(1’S,2''R)(2''-羟基-1’,2’二苯基乙基)氨基］-3,4-二酮环丁烯硫醇钠的表征与应用 

针对2\[(1’S,2’R)(2’羟基1’,2’二苯基乙基)氨基\]3,4二酮环丁烯硫醇钠的结构，通过元素分析，红外光谱及核磁共振进行了表征，并考察了它与常见金属离子的作用。实验表明，该化合物是一个优良的手性配体。     

不对称合成4-氧代-2,4-二苯基-丁酸酯

手性醇衍生的α-重氮苯乙酸酯与N-(苯乙烯基)-吗啉在铜盐催化下的反应，能够以高度的化学产率制备手性的4-氧代-2，4-二苯基-丁酸酯，产物中两种非对映异构体的比例达到2：1．     

Mathematical modeling of salt-gradient ion-exchange simulated moving bed chromatography for protein separations

The salt-gradient operation mode used in ion-exchange simulated moving bed chromatography (SMBC) can improve the efficiency of protein separations. A detailed model that takes into account any kind of adsorption/ion-exchange equilibrium, salt gradient, size exclusion, mass transfer resistance, and port periodic switching mechanism, was developed to simulate the complex dynamics. The model predictions were verified by the experimental data on upward and downward gradients for protein separations reported in the literature. All design and operating parameters (number, configuration, length and diameter of columns, particle size, switching period, flow rates of feed, raffinate, desorbent and extract, protein concentrations in feed, different salt concentrations in desorbent and feed) can be chosen correctly by numerical simulation. This model can facilitate the design, operation, optimization, control and scale-up of salt-gradient ion-exchange SMBC for protein separations.     

Enantioselective assay of S（＋）－ and R（－）－propafenone in human urine by using RP－HPLC with pre－column chiral derlvatization

The enantioselective assay for S(+)- and R(-)-propafenone (PPF) in human urine that developed in this work involves extraction of propafenone from human urine and using S(+)-propafenone as internal standard, chiral derivatization with 2,3,4,6-tetra-O-beta-D-glucopranosyl isothiocyanate, and quantitation by an RP-HPLC system with UV detection (lambda=220 nm). A baseline separation of propafenone enantiomers was achieved on a 5-microm reverse phase ODS column, with a mixture of acetic acid (25:12:0.02,v/v) as mobile phase. There was good linear relationship from 24.9 ng/ml to 1875.0 ng/ml for both of enantiomers. The regression equations of the standard curves based on C(S-PPF) (or C(R-PPF)) versus ratio of A(S-PPF)/A(S) (or A(R-PPF)/A(S)) were y=0.0032x-0.081, (r=0.999) for S-PPF and y=0.0033x+0.0039, (r=0.998) for R-PPF, respectively. The method's limit of detection was 12.5 ng/ml for both enantiomers, and the method's limit of quantitation was 28.2+/-0.52 ng/ml for S-PPF, 30.4+/-methanol:water:glacial 0.53 ng/ml for R-PPF (RSD<8%, n=5). The analytical method yielded average recovery of 98.9% and 100.4% for S-PPF and R-PPF, respectively. The relative standard deviation was no more than 6.11% and 6.22% for S-PPF and R-PPF, respectively. The method enabled study of metabolism of S(+)- and R(-)-propafenone in human urine. The results from 7 volunteers administered 150 mg racemic propafenone indicated that propafenone enantiomers undergo stereoselective metabolism and that in the human body, S(+)-propafenone is metabolized more extensively than R(-)-propafenone.     

(S)-(─)-α-苯乙胺萃取过程的研究

提出采用萃取法回收苯乙胺的工艺方案,考察了多种萃取剂的萃取性能,确定了氯仿作萃取剂的操作条件。根据实验和计算表明本方案苯乙胺的萃取收率可达９７％以上,苯乙胺的总回收率可达８７％以上。     

用手性配体改性的铝锂试剂对脂肪酮的不对称还原

利用手性一元醇作用辅助配体,与１,２,５,６－二丙酮甘露醇共同修饰ＬｉＡｌＨ４对脂肪酮进行对映选择还原,得到光学活性产物８个,通过与α－乙酰摒在－ｌ－丙酰氯作用生成非对映异构体体酯,经气相色谱分析,光学产率为２．７％～３０％。