氨基酸对映体的手性拆分

氨基酸对映体的分离是生命科学的基础,主要方法有高效毛细管电泳法、高效液相色谱法、薄层色谱法和气相色谱法等,高效液相色谱法是广泛应用的手性氨基酸拆分方法。本文介绍了间接法和直接法手性拆分的分离机理,并详细介绍了Pirkle手性固定相、胶束手性固定相、包合手性固定相、配体交换手性固定相、蛋白质手性 j固定相等5类手性固定相的应用。     

毛细管电泳技术在手性拆分中的最新进展和应用研究

主要对毛细管电泳在手性拆分领域的应用和发展进行了综述,并分析比较了用于毛细管电泳的不同手性拆分剂,显示出毛细管电泳是用于手性拆分的一种高效、快速、简便的分离手段。     

高效毛细管电泳在手性药物分析中的应用

近年来,手性药物的毛细管电泳拆分技术发展迅速,文章综述了毛细管电泳法拆分手性药物的机理、方法及应用,并重点介绍近年来各类手性选择剂的发展现状。     

Eupergit手性配体交换色谱固定相的制备及应用

介绍了以Eupergit C 250L为载体,L-羟脯氨酸盐为手性配体,通过两者间的"一步交联反应",制备出一种新型的Eupergit手性配体交换固定相。交联反应过程简单、高效、副反应少。尝试通过此大颗粒的Eupergit手性配体固定相对丝氨酸手性对映异构体进行拆分,得到了良好的拆分结果。为将来在工业领域内,通过使用制备型拆分柱来拆分手性氨基酸的设想提供了有利的技术支持。     

手性配体交换毛细管电泳研究进展

综述了近年来基于手性配体交换原理的毛细管电泳在分离手性化合物中的应用,并讨论了如温度、pH等影响分离度的因素.     

HPLC法和HPCE法在手性分子拆分领域的应用

对HPLC（高效液相色谱）法和HPCE（高效毛细管电泳）法在手性拆分领域的应用和分展进行了综述,主要论述手性HPLC拆分法中各种手性固定相的情况和手性HPCE拆分法中手性添加剂的选择,并对该领域未来的发展方向作出展望,显示出高效液相色谱和毛细管电泳是进行手性拆分的高效、快速、简便的分离手段。     

DL-氨基酸在新型配体交换色谱固定相上的手性拆分

设计和制备了 1 ,2 ,3,4-四氢 - 3-异喹啉羧酸衍生物手性选择子 ,用作手性配体交换色谱固定相 ,拆分了某些氨基酸对映体。     

手性氨基醇的合成及应用

对氨基酸(醛、酮)的还原或加成、氨基酸酯的还原、环氧乙烷类叠氮化还原合成手性氨基醇的方法进行了综述,讨论手性氨基醇作为配体催化潜手性化合物方面的应用.     

HPCE法手性拆分(R)-和(S)-3-羟基戊二酸乙酯

以β-环糊精(β-CD)为手性选择剂,采用毛细管区带电泳(CZE)对(R)-和(S)-3-羟基戊二酸乙酯进行手性拆分。通过考察手性选择剂浓度、电泳缓冲液pH、柱温以及分离电压对分离的影响,建立了比较理想的毛细管电泳手性拆分方法。在30 mmol/Lβ-CD、pH 5.0、柱温25℃以及分离电压20 kV分离条件下,(R)-和(S)-3-羟基戊二酸乙酯得到了完全分离。该分离方法具有较好的重复性和稳定性。     

双齿型L-脯氨酸手性配体交换色谱固定相的合成及对氯苯那敏的拆分

以3-氨丙基三乙氧基硅烷和三聚氯氰为连接臂合成了一种新型的双齿型L-脯氨酸手性配体交换色谱固定相,并利用元素分析进行了表征。本手性配体交换色谱固定相成功地拆分了手性药物氯苯那敏,并详细考察了流动相p H、中心金属离子浓度和缓冲溶液浓度以及柱温等对拆分效果的影响,得到了较佳拆分条件。在较佳拆分条件下,氯苯那敏的分离度可达2.87。同时对分离机理进行了简单的探讨。     

可溶性淀粉在毛细管电泳手性分离中的应用

非环化糖类手性选择剂是一种新型的手性选择剂,能对一些难以用环糊精类化合物分离的手性药物对映体进行分离,本文以非环化糖类中的可溶性淀粉作为手性选择剂,探讨了其在毛细管电泳手性药物分离中的优化条件。     

环糊精及其衍生物在高效毛细管电泳手性拆分中的应用

高效毛细管电泳 ( HPCE)在手性拆分中的应用近年受到普遍关注。含有手性添加剂环糊精 ( CD)及其衍生物的毛细管区带电泳 ( CZE)和胶束电动毛细管色谱 ( MECC)拆分体系方面研究非常活跃。综述了 CD- CZE和 CD-MECC体系 ,探讨了各体系的拆分机理和各实验条件对拆分结果的影响。     

Chiral Bis(N‐sulfonylamino)phosphine‐ and TADDOL‐Phosphite‐Oxazoline Ligands: Synthesis and Application in Asymmetric Catalysis

A series of N,P‐ligands has been prepared, containing a chiral oxazoline ring and as a second chiral unit a bis(N‐sulfonylamino)phosphine group embedded in a diazaphospholidine ring or a cyclic phosphite group derived from TADDOL. These modular ligands are readily synthesized from chiral amino alcohols and chiral 1,2‐diamines or TADDOLs. Palladium and iridium complexes derived from these ligands were found to be efficient catalysts for enantioselective allylic alkylation and olefin hydrogenation, respectively.     

Asymmetric Intramolecular C?H Insertion of α‐Diazoacetamides in Water by Dirhodium(II) Catalysts Derived from Natural Amino Acids

The asymmetric dirhodium(II)‐catalyzed intramolecular C H insertion of α‐diazo acetamides in water is described for the first time. The use of natural α‐amino acids as chiral ligands allowed the preparation of novel dirhodium(II) homochiral complexes by a simple procedure consisting of the in situ ligand exchange starting from dirhodium tetraacetate. The catalytic system was further reused up to 7 cycles and β‐lactams were obtained in good yields and enantiomeric excess.     

氨基酸金属有机框架的研究进展

氨基酸金属有机框架是指含有氨基酸单元的有机配体与金属离子共同参与合成的具有周期性结构的材料。氨基酸作为蛋白质的组成成分,具有绿色环保、生物相容性良好、种类多样、价格低廉等优点,将其引入金属有机框架（MOFs）可以赋予材料特殊的柔性结构、丰富的活性位点、优良的应用性能等特征。该文综述了氨基酸MOFs的结构维度分类,介绍了氨基酸MOFs的主要合成方式,包括溶剂热法、机械化学合成法、微波加热辅助法,进一步阐述了材料的性能调控,重点介绍了这类材料在手性拆分、催化、吸附等领域的应用。最后,通过分析当前氨基酸金属有机框架材料存在的稳定性不好、结构难以预测等问题,对其未来在生物医药领域的研究重点进行了展望。     

毛细管电泳在手性物质分离中的应用

综述了近年来毛细管电泳在手性物质分离中的应用情况。对手性拆分模式及几种主要手性选择剂简明地作了介绍。     

Chiral diphosphine and monodentate phosphorus ligands on a spiro scaffold for transition-metal-catalyzed asymmetric reactions

The preparation of chiral compounds in enantiomerically pure form is a challenging goal in modern organic synthesis. The use of chiral metal complex catalysis is a powerful, economically feasible tool for the preparation of optically active organic compounds on both laboratory and industrial scales. In particular, the metals coordinated by one or more chiral phosphorus ligands exhibit amazing enantioselectivity and reactivity. Many chiral phosphorus ligands have been synthesized and used in transition-metal-catalyzed asymmetric reactions in past decades. However, a large number of reactions still lack effective chiral ligands, and the enantioselectivities in many reactions are substrate-dependent. The development of effective chiral phosphorus ligands, especially ligands having novel chiral backbones, is still an important task in the area of asymmetric catalysis. Molecules containing a spirocyclic framework are ubiquitous in nature. The synthesis of molecules with this spiro structure can be traced back to 100 years ago. However, the use of this spirocyclic framework to construct chiral phosphorus ligands is a recent event. This Account outlines the design and synthesis of a new family of chiral spiro phosphorus ligands including spiro diphosphines and spiro monodentate phosphorus ligands with 1,1'-spirobiindane and 9,9'-spirobifluorene backbone and their applications in transition-metal-catalyzed asymmetric hydrogenation and carbon-carbon bond formation reactions. The chiral spiro diphosphine lgands SDP with a 1,1'-spirobiindane backbone and SFDP with a 9,9'-spirobifluorene backbone, and the spiro monophosphorus ligands including phosphoramidites, phosphites, phosphonites, and phospholane with a 1,1'-spirobiindane backbone were synthesized in good yields from enantiomerically pure 1,1'-spirobiindane-7,7'-diol and 9,9'-spirobifluoren-1,1'-diol. The ruthenium complexes of chiral spiro diphosphine ligands proved to be very effective catalysts for asymmetric hydrogenations of ketones, alpha-arylaldehydes and alpha,beta-unsaturated acids. The rhodium complexes of chiral spiro monophosphorus ligands are highly enantioselective for the asymmetric hydrogenations of alpha- and beta-dehydroamino acid derivatives, alpha-arylethenyl acetamides and non- N-acyl enamines. The spiro monophosphorus ligands were demonstrated to be highly efficient for the Rh-catalyzed asymmetric addition of arylboronic acids to aldehydes and N-tosylarylimines, Pd-catalyzed asymmetric allylation of aldehydes with allylic alcohols, Cu-catalyzed asymmetric ring opening reactions with Grignard reagents, and Ni-catalyzed asymmetric hydrovinylation of styrene derivatives with ethylene. The chiral spiro phosphorus ligands show high enantioselectivities for a wide range of transition-metal-catalyzed asymmetric reactions. In most of these transformations, the enantioselectivities of spiro phosphorus ligands are superior to those obtained by using the corresponding phosphorus ligands with other backbones. These results arise from the intriguing chiral inducement of spiro structures of the ligands.     

Synthesis and Characterization of Privileged Monodentate Phosphoramidite Ligands and Chiral Brønsted Acids Derived from d-Mannitol

The synthesis of several novel chiral phosphoramidite ligands (L1–L8) with C₂ symmetric, pseudo C₂ symmetric secondary amines and chiral Brønsted acids 1a,b has been achieved. These chiral auxiliaries were obtained from commercially available d-mannitol, and secondary amines in moderate to excellent yields. Excellent diastereoselectivites of ten chiral auxiliaries were obtained. The chiral phosphoramidite ligands and chiral Brønsted acids were fully characterized by spectroscopic methods.     

2-O-（2-羟丁基）-β-环糊精在非水毛细管电泳中拆分手性药物的研究

以2—O-（2一羟丁基）-β-环糊精（HB-β-CD）为手性选择剂,对普萘洛尔、山茛菪碱、异丙嗪3种碱性手性药物进行非水毛细管电泳拆分。考察了有机溶剂、电解质、手性选择剂浓度以及pH值对分离度的影响。研究结果表明：普萘洛尔、山莨菪碱和异丙嚷3种碱性手性药物全部达到基线分离。可见HB-β-CD在碱性药物拆分方面具有特殊能力,为碱性手性药物的拆分提供了一种准确、简便的分析方法。