Enantiomer最新文献

英文中文

Real-time assessment of enantiomeric purity via a polarimetric/absorption detector response function. 通过偏振/吸收检测器响应函数实时评估对映体纯度。

Enantiomer

Pub Date : 2002-01-01 DOI: 10.1080/10242430210702

Sean W. Linder, Gary W. Yanik, E. Francotte, D. R. Bobbitt

The development of methodology appropriate for the rapid and precise assessment of enantiomeric purity is a critical need in the life sciences with impact in a number of areas including biomedical research, biotechnology, and pharmaceutical science. Real-time assessment of enantiomeric purity is critical to decisions related to possible product purity and/or the need for, and the type of additional processing. Recently, we have shown that laser-based polarimetric detection, in combination with ultraviolet detection, can be used to assess enantiomeric purity in real-time as an adjunct to the separation process. A mass-independent response function is obtained from the ratio of the normalized polarimetric signal relative to the normalized UV signal. This response ratio will be shown to be equivalent to the enantiomeric excess and independent of concentration and chromatographic resolution. The methodology will be evaluated as a function of injected mass, enantiomeric excess, chromatographic resolution, and peak asymmetry.

对映体纯度的快速和精确评估方法的发展是生命科学领域的一个关键需求，对包括生物医学研究、生物技术和制药科学在内的许多领域都有影响。对映体纯度的实时评估对于决定可能的产品纯度和/或额外处理的需要和类型至关重要。最近，我们已经证明了基于激光的偏振检测，结合紫外线检测，可以用来实时评估对映体的纯度，作为分离过程的辅助手段。从归一化极化信号相对于归一化紫外信号的比值得到了一个质量无关的响应函数。该响应比将显示为与对映体过量相等，与浓度和色谱分辨率无关。该方法将作为注入质量、对映体过量、色谱分辨率和峰不对称性的函数进行评估。

引用次数: 2

Concise synthesis and enzymatic resolution of L-(+)-homophenylalanine hydrochloride. L-(+)-同苯丙氨酸盐酸盐的简明合成及酶解。

Enantiomer

Pub Date : 2002-01-01 DOI: 10.1080/10242430210706

Hua Zhao, R. G. Luo, D. Wei, S. Malhotra

The N-acetyl-homophenylalanine ethyl ester was synthesized by a simple three-step-reaction strategy. L-(+)-homophenylalanine hydrochloride with 98% ee was obtained through a kinetic resolution process using industrial enzyme alcalase. Compared with other methods, this strategy has the advantage of economical and simple procedure giving high product optical purity.

采用简单的三步反应策略合成了n -乙酰基同苯丙氨酸乙酯。以工业酶alcalase为原料，采用动力学拆分工艺制备了纯度为98%的L-(+)-同苯丙氨酸盐酸盐。与其他方法相比，该方法具有经济、操作简单、产品光学纯度高的优点。

引用次数: 17

Absolute stereochemistry of chiral C60 fullerene bis-adducts. 手性C60富勒烯双加合物的绝对立体化学。

Enantiomer

Pub Date : 2002-01-01 DOI: 10.1080/10242430210704

Kazuhiro Yoshida, S. Ōsawa, K. Monde, Masataka Watanabe, N. Harada

To determine the absolute configuration of chiral fullerene bis-adducts, we have studied the double Bingel reaction of C60 with chiral tether (2S,3S)-(-)-9 derived from (R,R)-(+)-tartaric acid, and have succeeded in isolating two possible chiral bis-adducts 10a (5%) and 10b (2%) in addition to the Cs-symmetrically added derivative 10c (40%). The CD spectra of chiral bis-adducts [CD(+)281]-10a and [CD(-)281]-10b show very intense Cotton effects, which are almost of mirror image, indicating that their chiral C60 pi-electron systems are enantiomeric each other. The 1H and 13C NMR spectra of 10a and 10b indicate that they have C2-symmetrical structures, and the vicinal coupling constants between two equivalent protons H-2 and H-2' were determined as 1.2 Hz for 10a and 1.8 Hz for 10b, respectively by the 13C satellite band method. From the conformational analyses, the absolute configurations of these chiral C60 fullerene bis-adducts were unambiguously determined as [CD(+)281]-(S,S,fC)-10a and [CD(-)281]-(S,S,fA)-10b, respectively.

为了确定手性富勒烯双加合物的绝对构型，我们研究了C60与(R,R)-(+)-酒石酸衍生的手性链(2S,3S)-(-)-9的双宾格尔反应，并成功分离出两种可能的手性双加合物10a(5%)和10b(2%)以及cs对称添加的衍生物10c(40%)。手性双加合物[CD(+)281]-10a和[CD(-)281]-10b的CD谱显示出很强的棉花效应，两者几乎是镜像，表明它们的手性C60 π电子体系是对映体。10a和10b的1H和13C核磁共振谱表明它们具有c2对称结构，并用13C卫星波段法测定了两个等效质子H-2和H-2′之间的邻近耦合常数，10a为1.2 Hz, 10b为1.8 Hz。通过构象分析，确定了这些手性C60富勒烯双加合物的绝对构型分别为[CD(+)281]-(S,S,fC)-10a和[CD(-)281]-(S,S,fA)-10b。

引用次数: 9

Enantiopure spiro[3.3]heptane-2,6-dicarboxylic acid. 对映纯螺[3.3]庚烷-2,6-二羧酸。

Enantiomer

Pub Date : 2002-01-01 DOI: 10.1080/10242430210705

Hongzhi Tang, H. Miura, Y. Kawakami

Using chiral HPLC and 13C NMR analyses, the optical purity of (+)-spiro[3.3]heptane-2,6-dicarboxylic acid (1) obtained by the known diastereomer method with brucine was first clarified to be 90% e.e., which was conventionally considered to be 100% e.e. Among the ester derivatives synthesized, dicinnamyl spiro[3.3]heptane-2,6-dicarboxylate (2) was found to show high optical separation ability on the chiral HPLC with cellulose phenyl carbamate stationary phase eluting with hexane/2-propanol (10/1, v/v) at a flow rate of 0.4 ml/min at 35 degrees C (separation factor, a, 1.14), and the isolated optically pure (+)- and (-)-2 show [alpha]D26 of + 1.84 degrees (c = 1.74, CHCl3) and -1.84 degrees (c = 1.74, CHCl3), respectively. Acidic hydrolysis of optically pure (+)-/(-)-2 without racemization yielded optically pure (+)-/(-)-1, exhibiting [phi]405(270 = + 21.1 degrees ([phi]D27 = +9.1 degrees) (c = 5.33, acetone) and [phi]405(27) = -21.1 degrees ([phi]D27 -9.1 degrees) (c = 5.32, acetone), respectively.

通过手性高效液相色谱和13C核磁共振分析，通过已知的与马钱子碱非对映体方法得到的(+)-螺旋[3.3]庚烷-2,6-二羧酸(1)的光学纯度首次被澄清为90% e.e，而传统上认为是100% e.e。采用纤维素苯基氨基甲酸酯固定相，正己烷/2-丙醇(10/1,v/v)洗脱，流速为0.4 ml/min, 35℃(分离因子a, 1.14)，手性高效液相色谱法(HPLC)发现双苯基螺[3.3]庚烷-2,6-二羧酸酯(2)具有良好的光学分离能力，分离得到的光纯(+)-和(-)-2的[α]D26分别为+ 1.84度(C = 1.74, CHCl3)和-1.84度(C = 1.74, CHCl3)。光纯(+)-/(-)-2无外消旋的酸水解得到光纯(+)-/(-)-1，分别表现为[phi]405(270 = + 21.1度([phi]D27 = +9.1度)(c = 5.33，丙酮)和[phi]405(27) = -21.1度([phi]D27 -9.1度)(c = 5.32，丙酮)。

引用次数: 3

Optical resolution of 5-alkyl-delta-valerolactones and synthesis of optically active 5-fluoroalkanols. 5-烷基-三角戊内酯的光学拆分及光学活性5-氟烷醇的合成。

Enantiomer

Pub Date : 2002-01-01 DOI: 10.1080/10242430210707

A. Riswoko, Y. Aoki, T. Hirose, H. Nohira

Optical resolutions of 5-alkyl-delta-valerolactones were carried out by derivatization to the diastereomeric amides, in which (R)-(+)-1-(1-naphthyl)ethylamine or (S)-(-)-1-phenylethylamine were used as resolving agents. Optically active 5-fluoroalkanols, useful intermediates for fluorinated ferroelectric liquid crystals, were derived from the resolved lactones in four steps without racemization.

以(R)-(+)-1-(1-萘基)乙胺或(S)-(-)-1-苯乙胺为拆分剂，通过衍生化法制备了5-烷基- δ戊内酯的非对映体酰胺。光活性的5-氟烷醇是氟化铁电液晶的有用中间体，在没有外消旋的情况下由内酯分解得到。

引用次数: 1

Chemical process evolution of efavirenz, a potent non-nucleosidal HIV reverse transcriptase inhibitor. 有效的非核苷类HIV逆转录酶抑制剂依非韦伦的化学过程演化。

Enantiomer

Pub Date : 2000-06-13 DOI: 10.1002/CHIN.200024280

C. Chen, L. Tan

引用次数: 9

Developing a chiral toolbox for asymmetric catalytic reactions. 开发用于不对称催化反应的手性工具箱。

Enantiomer

Pub Date : 2000-05-30 DOI: 10.1002/CHIN.200022284

X. Zhang

During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. The research in our group addresses fundamental and practical problems in this field by developing a diverse set of chiral ligands that combine with transition metals to form highly enantioselective catalysts. Families of tridentate ligands have been developed for the enantioselective hydrogenation of unfunctionalized substrates. In addition, we have developed several new bidentate phosphine ligands for asymmetric catalysis. The common feature of these ligands are that they contain rigid aromatic backbones or ring structures which restrict conformational flexibility of the ligands. Several asymmetric reactions have been studied: asymmetric hydrogenation of functionalized substrates such as N-acylaminoacrylic acids, enamides and enol acetates; asymmetric hydrogenation of simple ketones, and imines; and asymmetric carbon-carbon bond forming reactions. In addition, we have designed and synthesized several novel chiral monophosphines for asymmetric catalytic reactions. Transition metal complexes with these monophosphines have also been developed for asymmetric transformations.

在过去的几十年里，化学家们在发现人造催化剂以进行具有挑战性的不对称转化方面取得了重大进展。我们小组的研究通过开发一套不同的手性配体，与过渡金属结合形成高度对映选择性催化剂，解决了该领域的基础和实际问题。三齿配体家族被开发用于非功能化底物的对映选择性加氢。此外，我们还开发了几种新的双齿膦配体用于不对称催化。这些配体的共同特点是它们含有刚性的芳骨架或环结构，这限制了配体的构象灵活性。研究了几种不对称反应:功能化底物如n -酰基氨基丙烯酸、酰胺和烯醇乙酸酯的不对称加氢;简单酮和亚胺的不对称加氢反应不对称碳碳键形成反应。此外，我们还设计并合成了几种用于不对称催化反应的新型手性单膦。与这些单膦的过渡金属配合物也被用于不对称转化。

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引用次数: 22

Enantioseparation of aminoglutethimide with cyclodextrins in capillary electrophoresis and studies of selector-selectand interactions using NMR spectroscopy and electrospray ionization mass spectrometry. 毛细管电泳环糊精对氨基乙硫胺对映体分离及核磁共振和电喷雾质谱研究选择-选择和相互作用。

Enantiomer

Pub Date : 2000-01-01

B Chankvetadze, M Fillet, N Burjanadze, D Bergenthal, C Bergander, H Luftmann, J Crommen, G Blaschke

The enantiomers of aminoglutethimide [2-(p-aminophenyl)-2-ethylglutarimide, AGT] can be resolved in CE using all of three most commonly used native cyclodextrins (CD): alpha-, beta-, and gamma-CDs. The migration order of the enantiomers was opposite using beta-CD compared to alpha- and gamma-CDs as chiral selectors. In order to examine some underlying mechanisms of the chiral recognition the interaction of AGT with the chiral selectors was studied with one- and two-dimensional NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). The Job's and Scott's plots constructed based on the complexation-induced chemical shifts (CICS) observed in NMR spectra provided some preliminary information on the stoichiometry of the intermolecular complexes but did not seem to be absolutely reliable perhaps because the self-association of the analyte molecules and the formation of multiple type selectand-selector complexes. Therefore, an attempt was made to characterize the complexes using ESI-MS. This technique provided information on the stoichiometry and relative affinity constants of selector-selectand complexes. The information on the structure of complexes in the solution was obtained using one-dimensional rotating frame nuclear Overhauser enhancement (1D-ROESY) NMR spectroscopic studies. Significant differences were observed between the structures of the AGT complexes with beta- and gamma-CD.

氨基乙酰亚胺的对映体[2-(对氨基苯基)-2-乙基戊二酰亚胺，AGT]可以用三种最常用的天然环糊精(CD): α -， β -和γ - cds在CE中分离。与- cd和- cd作为手性选择器相比，- cd对映体的迁移顺序相反。为了研究AGT手性识别的一些潜在机制，利用一维和二维核磁共振波谱和电喷雾电离质谱(ESI-MS)研究了AGT与手性选择子的相互作用。基于核磁共振光谱中观察到的络合诱导化学位移(CICS)构建的Job’s和Scott’s图提供了一些关于分子间络合物化学计量学的初步信息，但似乎不是绝对可靠的，这可能是因为分析物分子的自结合和多种类型选择-选择络合物的形成。因此，尝试用ESI-MS表征配合物。该技术提供了选择-选择复合物的化学计量学和相对亲和常数的信息。利用一维旋转框架核磁共振波谱(1D-ROESY)研究了溶液中配合物的结构信息。与-和- cd的AGT复合物的结构有显著差异。

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引用次数: 0

Synthesis of enantiomerically pure C2-symmetric 4-pyrrolidinopyridine derivative as a chiral acyl transfer catalyst for the kinetic resolution of secondary alcohols 对映体纯c2对称4-吡咯烷二吡啶衍生物手性酰基转移催化剂的合成

Enantiomer

Pub Date : 2000-01-01

Naraku, Shimomoto, Hanamoto, Inanaga

The first chiral C2-symmetric 4-pyrrolidinopyridine (PPY) derivative was synthesized in an enantiomerically pure form and successfully utilized as a chiral nucleophilic catalyst for the kinetic resolution of secondary alcohols leaving one enantiomer with high selectivity factors (up to s = 13.5).

以对映体纯形式合成了首个手性c2对称4-吡咯烷二吡啶(PPY)衍生物，并成功地作为手性亲核催化剂用于仲醇的动力学拆分，得到一个具有高选择性因子(s = 13.5)的对映体。

引用次数: 0

Lanthanide complexes as smart CD probes for chirality sensing of biological substrates. 镧系配合物作为智能CD探针用于生物底物手性传感。

Enantiomer

Pub Date : 2000-01-01

H Tsukube, S Shinoda

Lanthanide tris(beta-diketonates) and porphyrinates acted as effective circular dichroism (CD) probes for chirality sensing of neutral and zwitterionic guests. They were electrically neutralized but formed highly coordinated 1:1 complexes with various guests. When a chiral, non-chromophoric guest was combined with a chromophoric lanthanide probe, the resulting highly coordinated complex exhibited characteristic CD signal, the sign of which was dependent on the absolute configuration of the bound guest. Since there are wide variations of coordinating ligands and lanthanide centers, lanthanide coordination chemistry offers great possibilities for the design of new CD chirality sensory systems especially for biologically important guests.

镧系三(β -二酮酸酯)和卟啉酸酯是有效的圆二色性(CD)探针，用于检测中性和两性离子客体的手性。它们被电中和，但与各种客人形成高度协调的1:1复合物。当手性非显色客体与显色镧系探针结合时，得到的高度配位配合物表现出特征CD信号，其符号依赖于结合客体的绝对构型。由于配位配体和镧系元素中心有很大的变化，镧系元素配位化学为设计新的CD手性感觉系统提供了很大的可能性，特别是对于生物学上重要的客体。

引用次数: 0

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