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1.
在过氧化氢酶和氧气存在下,固定化D-氨基酸氧化酶(D-AAO)对映选择性催化DL-氨基酸中的D-对映体氧化脱氨为相应酮酸,L-对映体保留.研究了D-AAO的底物特异性并对反应条件进行了优化.结果表明:D-AAO具有较宽的底物谱,能够催化疏水性α-氨基酸的D-对映体氧化脱氨.在最优反应条件下,D-AAO催化DL-2-氨基丁酸、DL-2-氨基戊酸去消旋化,L-2-氨基丁酸、L-2-氨基戊酸的收率分别为48%和47%,ee分别为99.5%和99.8%.进一步地利用Pd-C/HCOONH4催化氧化脱氨过程中产生的亚氨基酸原位还原,有效提高了L-2-氨基丁酸、L-2-氨基戊酸的收率并保持高的光学纯度.  相似文献   

2.
徐红梅 《分子催化》2013,27(3):212-217
提出了一个5-硝基水杨醛催化L-酪氨酸甲酯消旋化的新方法并推测了L-酪氨酸甲酯的消旋机理.在乙腈/磷酸盐缓冲液(pH 7.5)中,5-硝基水杨醛催化L-酪氨酸甲酯消旋为DL-酪氨酸甲酯,消旋率100%,消旋收率93%.优化了Alcalase 2.4L催化DL-酪氨酸甲酯对映选择性水解的反应条件.30℃下,在叔丁醇/磷酸盐缓冲液(pH 7.5)中,Alcalase 2.4L催化DL-酪氨酸甲酯对映选择性水解为L-酪氨酸和D-酪氨酸甲酯.在酶催化水解过程中,L-酪氨酸形成沉淀,容易通过简单的过滤进行分离.D-酪氨酸甲酯在碱性条件下水解为D-酪氨酸,收率91%,ee97%.  相似文献   

3.
建立了一个新颖的用于产生D-脯氨酸的发酵-生物转化过程.发酵过程中,以DL-脯氨酸为发酵前体,类产碱假单胞菌XW-40利用L-对映体诱导产生脯氨酸脱氢酶,D-对映体完全保留.在最优条件下,发酵阶段产生6 g/L D-脯氨酸.生物转化过程中,细胞不经分离,发酵液直接作为反应介质.采用分批补料策略实现DL-脯氨酸中L-对映体的转化.DL-脯氨酸单批补料浓度为10 g/L,补料次数达到5批.通过发酵和生物转化的级联,累积的D-脯氨酸浓度达到31 g/L,ee99%.推测了生物转化过程中D-脯氨酸产生的反应机理.  相似文献   

4.
L-乳酸与三氟乙酸酐反应, 生成L-α-三氟乙酰氧基乳酸, 再与二氯亚砜作用, 合成新的手性试剂----L-α-三氟乙酰氧基丙酰氯. 它与DL-α-苯乙胺及三种DL-α-氨基酸反应, 生成相应的非对映异构体酰胺, 在以Carbowax为固定相的毛细管柱上进行气相色谱拆分. 以相应的L-胺及L-氨基酸在相同条件下进行比较, 发现D-异构体的保留时间较短 .  相似文献   

5.
研究了2-氨基-2'-羟基-1,1'-联萘衍生的有机小分子催化剂催化的直接羟醛缩合反应. 以丙酮为反应物时最好, 得到了99%的收率. 以环酮为底物时, 最高得到99∶1的非对映选择性, 89%的对映选择性.  相似文献   

6.
研究了2-氨基-2'-羟基-1,1'-联萘衍生的有机小分子催化剂催化的直接羟醛缩合反应.以丙酮为反应物时最好,得到了99%的收率.以环酮为底物时,最高得到99:1的非对映选择性,89%的对映选择性.  相似文献   

7.
以系列L-氨基酸衍生物作为手性修饰剂,研究了三苯基膦(tpp)稳定的1.0%Ru/γ-Al2O3催化剂催化芳香酮多相不对称加氢,考察了稳定剂种类、修饰剂种类、金属负载量、底物浓度、温度、压力等因素对不对称加氢反应的影响。结果表明,L-氨基酸衍生物对1.0%Ru/γ-Al2O3/2tpp催化剂具有较好的修饰作用,在优化反应条件下芳香酮加氢反应的对映选择性达33%-81%,苯乙酮加氢反应的对映选择性可达70%。  相似文献   

8.
研究了三氟乙酸(TFA)对各种L-α-氨基酸催化环己酮与对硝基苯甲醛的不对称直接Aldol反应的影响.结果表明:在TFA作用下,所测试的绝大部分氨基酸的催化性能都有显著变化,多数情况下能提高收率和对映选择性;对非对映选择性的影响无明显规律.  相似文献   

9.
 尽管含芳香基等较大取代基团的底物能被生物转化为高对映体纯手性有机硅醇,但生物催化其他底物还原反应的产物收率及对映体选择性均较低. 作者筛选到一株能高效催化羰基/羟基不对称转化的酵母菌株,探讨了用固定化酵母细胞高效催化乙酰基三甲基硅烷不对称还原制1-三甲基硅乙醇的可能性,系统研究了培养基碳源及其浓度对该反应的影响. 发现在水/正己烷两相体系中,固定化酵母细胞能催化乙酰基三甲基硅烷不对称还原成1-三甲基硅乙醇. 可通过调节培养基碳源的种类及其浓度在一定程度上控制反应的产物收率及对映体选择性. 以最适碳源(3.0%麦芽汁)培养的酵母细胞催化该反应的产物收率和对映体过量值分别为91.3%和72.8%,远高于文献报道值.  相似文献   

10.
胡向平 《分子催化》2011,(6):485-488
将BoPhoz类膦-氨基膦配体应用在Rh-催化β-脱氢氨基酸酯的不对称氢化反应中,考察了配体结构及反应条件对反应结果的影响,并在优化的条件下研究了各种底物的适用范围,产物的对映选择性达81%ee.  相似文献   

11.
Susanna Branion 《合成通讯》2013,43(15):2121-2127
We report in detail the preparation of two substituted terephthalic acids: 2‐sulfomethylterephthalic acid (1) and 2‐phosphonoterephthalic acid (2). Efficient, short syntheses have been developed for both compounds. They are potentially useful monomers for construction of acid‐pendant polymer chains.  相似文献   

12.
New enantiomerically enriched bicyclic hydroxamic acids, 1-hydroxy-dihydro-1H-pyrrolo[1,2-a]imidazole-2,5(3H,6H)-diones, have been synthesized by the cyclocondensation of L-α-aminohydroxamic acids with keto acids in a highly chemo- and stereoselective manner. The cis configuration between the amino acid side chain and the methyl group at C7a in 1H-pyrrolo[1,2-a]imidazole-2,5-dione was unambiguously established by X-ray crystallographic analysis. This method could also be applied to the cyclocondensation with o-formylbenzoic acid, giving a tricyclic hydroxamic acid in a good yield.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.  相似文献   

13.
Although unsaturated fatty acids have long been known to accompany saturated fatty acids in most lipids, qualitative and quantitative determination of fatty acid patterns only became possible with the advent of modern analytical methods. Present day knowledge of the chemical structure, physical properties, and metabolism of unsaturated fatty acids provides the basis for the development of new concepts of their function. Thus unsaturated fatty acids crucially determine the properties of biological membranes. Moreover, essential fatty acids are precursors of prostaglandins.  相似文献   

14.
离子排斥色谱法分析有机酸和无机弱酸   总被引:3,自引:1,他引:2  
郜志峰  傅承光 《色谱》1996,14(3):237-238
 用非抑制型电导检测的离子排斥色谱法,以对甲苯磺酸为淋洗液,研究了柠檬酸、苹果酸、抗坏血酸、乙醇酸、甲酸、乙酸、丙酸及氢氟酸和碳酸的色谱分离及定量检测条件。  相似文献   

15.
芳基丙酮酸的合成   总被引:5,自引:0,他引:5  
本文报道用Meerwein芳基化反应由2-取代丙烯酸合成芳基丙酮酸的方法。 芳基重氮盐与2-乙酰氨基丙烯酸在丙酮-水溶液中、氯化铜存在下反应,迅速放出氮气,但从反应混合物中只分离到芳基丙酮酸1~9,产率中等。  相似文献   

16.
Direct oxidation of the 4,6‐O‐benzylidene acetal protecting group to C‐6 carboxylic acid has been developed that provides an easy access to a wide range of biologically important and synthetically challenging uronic acid and sugar amino acid derivatives in good yields. The RuCl3–NaIO4‐mediated oxidative cleavage method eliminates protection and deprotection steps and the reaction takes place under mild conditions. The dual role of the benzylidene acetal, as a protecting group and source of carboxylic acid, was exploited in the efficient synthesis of six‐carbon sialic acid analogues and disaccharides bearing uronic acids, including glycosaminoglycan analogues.  相似文献   

17.
The thermal behaviour of various substituted aminobenzoic acids(3-aminobenzoic acid (3-ABA), 4-aminobenzoic acid (4-ABA), 3-aminosalicylic acid(3-ASA), 4-aminosalicylic acid (4-ASA), and 5-aminosalicylic acid (5-ASA), as well as the‘parent’ benzoic acid (BA) and salicylic acid (SA) as reference substances, and possible decomposition products: 2-aminophenol (2-AP), 3-aminophenol (3-AP) and 4-aminophenol(4-AP) in the solid state has been examined. The various sets of isomers studied showed considerable and interesting differences. Most sublimed well before melting, generally with an increasing rate of mass loss beyond their very different melting points. The differences in behaviour of 4-ASA and 5-ASA were the most remarkable, with 5-ASA being far more stable and apparently not decarboxylating readily, while 4-ASA sublimed at temperatures below the melting point, becoming less stable and decarboxylating in the liquid form. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

18.
《Analytical letters》2012,45(7):509-514
Abstract

A simple method for the enantioselective determination of 2-halopropanoic acids and 2-halobutanoic acids with two bacterial 2-halo acid dehalogenases has been developed. L-2-Halo acid dehalogenase acts specifically on L-2-haloalkanoic acids, and DL-2-halo acid dehalogenase acts on both enantiomers of the acids. The dehalogenation was followed by determination of halogen ions released. Linear relationship was established between the absorbance at 460 nm, and the amounts of L-2-haloalkanoic acids (0.025-0.5 μmol) or the racemates (0.05-1.0 μmol). The D-isomers were estimated by subtracting the amounts of L-isomers from those of DL-2-haloalkanoic acids.  相似文献   

19.
ω-[(Arylphosphonomethyl)amino]alkylphosphonic and carboxylic acids are prepared in an easy work-up procedure, by addition of diethyl phosphite to in situ–generated arylideneaminoalkylphosphonic or carboxylic acids followed by hydrolysis with hydrochloric acid  相似文献   

20.
Abstract

A variety of substituted arylglyoxylic acids (2a?g) were synthesized via oxidation of the corresponding aryl-methylketones (1a–e) using selenium dioxide or Friedel–Crafts acylation of phenol (3) with ethyl chlorooxoacetate and further transformations. It was found that the arylglyoxylic acids (2) undergo facile unimolecular dissociation with loss of carbon monoxide to give the corresponding arylcarboxylic acids (7) under collisionally induced mass spectrometric conditions.  相似文献   

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