共查询到19条相似文献，搜索用时 109 毫秒
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我们通过手性二恶唑啉配体实现了铜催化的手性分子内O-H键插入omega-羟基-aIpha-重氮甲酸酯。高度对映体选择性分子内O-H键插入提供了一种不同大小和取代基的手性2-羧基环醚合成的有效方法。 相似文献
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以恶唑啉为导向基团 ,通过邻位锂化方便地高非对映选择性地合成了一系列平面手性二茂铁硫恶唑啉、硒恶唑啉和膦恶唑啉配体 .应用于 1 ,3 二苯基烯丙基醋酸酯的烯丙基烷基化反应 ,ee值最高可达 99%,膦氮配体在烯丙基胺化反应中 ,ee值最高也可达 97%.此外 ,发现中心手性起到了决定产物ee值和绝对构型的作用 ,平面手性和中心手性的匹配在取得高对映选择性上是重要的 .设计合成的一类平面手性二茂铁修饰的手性口袋型双膦配体 ,由于有平面手性的辅助而具有更有效的诱导效应 .这类配体在前手性亲核试剂的不对称烯丙基化生成季碳氨基酸衍生物构及alpha 位双取代季碳酮反应中 ,ee值最高分别可达到 75 %和 95 %.设计合成的 1 ,1’ 二茂铁膦氮配体 ,在单取代的烯丙基醋酸酯的钯催化区域选择性及对映选择性的烯丙基烷基化及胺化反应中 ,显示了非常高的反应活性、区域选择性和对映选择性 .配体中BINOL羟基由于和苄胺存在分子间氢键而对反应的选择性起到了关键作用 ,并从实验上给予了证明 相似文献
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对铑催化的1,6-烯炔环异构化反应进行了研究，这类反应具有较广的底物适应范围，在转化过程中，卤素发生了分子内转移。这类反应提供了一条新的立体选择性合成具有α-氯烯基结构的丁内酯、丁内酰胺、四氢呋喃、吡喃以及五元碳环等分子的方法。发展了两种不同的催化剂体系，即阳离子催化剂体系和中性催化剂体系。阳离子催化剂体系仅能催化顺式烯炔底物的环异构化，相反中性催化剂体系不但能催化顺反烯炔底物的环异构化，而且具有更广的底物适应范围。利用各种烯炔异构体，通过合适的控制实验对反应机理进行了研究。提出了涉及π-烯丙基铑中间体的可能机理，并且利用该机理对一些反应现象进行了解释。最后利用Suzuki偶联反应对产物进行了衍生。 相似文献
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本文通过紫外、红外和圆二色（CD）光谱表征考察了外在离心力场对非手性化合物异佛尔酮不对称氧化生成光学活性产物的影响。结果表明离心力场能够诱导产物的对映体过量,在顺时针和逆时针旋转力场中得到的产物CD230信号相反并随转速的增大而增大。作者推测,顺时针和逆时针圆周离心运动（轴矢量）结合地球在时空上的天然线性运动（极矢量）形成的左、右手螺旋运动的不对称作用可能是诱导反应对映体过量的力学原因。 相似文献
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以硅胶为载体,以硫酸盐为活性物质,采用浸渍法制备了一系列催化剂,催化对称性二醇的选择性酯交换反应,催化剂考察了活性物质负载量,浸泡时间和焙烧时间对催化剂活性的影响,结果表明以硫酸氢钠负载量1.5mmol,浸泡时间24小时,焙烧时间3小时的催化剂和以硫酸铈负载量0.3mmol,浸泡24小时,焙烧时间1小时的催化剂转化率和选择性最高。并验证了此催化剂对于对称性二醇的选择性酯交换反应具有很好的普遍适用性。 相似文献
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文章介绍了几种纤维素类手性拆分剂以及其制备方法相关分离机理,综述了纤维素手性拆分剂的分离机理及其应用,重点地介绍纤维素手性固定相和纤维素膜的应用。 相似文献
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综述了基于芯片电泳技术的手性分离进展。分别介绍了这一领域的进样、检测技术,所采用的手性选择剂,芯片制作材料及用于提高分离度的方法等,展望了手性分离在芯片电泳领域今后的发展方向。 相似文献
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Roger A. Grey Author Vitae 《Journal of The Franklin Institute》2006,343(3):214-222
The scientific theme for the 2005 Bower Award was Chemistry, specifically the field of Catalysis. The Franklin Institute, Philadelphia, Pennsylvania, awarded the 2005 Bower Award and Prize for achievement in Science to Henri B. Kagan for his seminal discovery of fundamental chemical principles that explain the impact of catalyst shape on its effectiveness in controlling chemical reactions, thus greatly simplifying the manufacture of pharmaceutically important compounds. Henri Kagan is widely recognized as a pioneer in the field of asymmetric catalysis. Starting in the early 1970s, his reports of the synthesis of the chiral bidentate diphosphine ligand and the demonstration of its use with soluble rhodium compounds to catalyze the efficient production of large enantiomeric excesses of chiral molecules in asymmetric hydrogenations has had far reaching effects on research in the field asymmetric catalysis. The concept of using chiral bidentate ligands of C2 symmetry has led the way for numerous developments in asymmetric catalysis. Later in 1986 his introduction of the concept and investigations into “nonlinear effects in asymmetric synthesis” using catalysts with chiral ligands that were not optically pure challenged the widely accepted assumption that the enantiomeric excess which is possible correlates linearly with the optical purity of the chiral ligands. He reported the first example in asymmetric catalysis where the optical purity of the product significantly exceeded the optical purity of the chiral ligand. 相似文献
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《国家科学评论(英文版)》2015,(2)
The expression of chirality in 2D molecular assemblies on solid surfaces has unique features compared to the analogous process in 1D and 3D supramolecular assemblies. Understanding the formation of chiral molecular assemblies on surfaces not only provides insight into the origin and transfer of chirality in many enantioselective processes, but also aids rational design and construction of chiral architectures and materials. his present contribution reviews recent studies on how chirality is induced and expressed on the surface at diferent levels, both from intrinsically chiral and achiral molecules. Furthermore, we discuss the regulation efect of some pivotal factors, for example, the chemical structure, the chiral auxiliary molecules,and the assembled environments, on the expression of chirality in molecular assembly. 相似文献
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研究了外在的离心力场对氯酸钠溶液结晶的影响,使用偏光显微镜考察了离心机的不同转速下,氯酸钠结晶过程中手性对称性破缺的统计结果.实验表明,作为一个物理因素,外在的离心力场能明显诱导氯酸钠溶液结晶的手性分布.当离心机转速较大时(如6000r/min),饱和溶液的结晶趋向于仅有一种构型——L型或D型,即能导致氯酸钠结晶的完全手性对称性破缺,且顺时针离心力场中D型晶体数量明显大于L型,而在逆时针离心力场中L型晶体数量却明显大于D型,并均随外力增大而效应增大.这些结果表明,外在离心力场可方向性地对氯酸钠溶液的不对称结晶过程产生重要影响. 相似文献
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运用螺旋理论推断秋水仙碱的构型 总被引：1，自引：0，他引：1
秋水仙碱是医治癌症的重要药物 ,其结构中不仅存在手性碳原子的构型问题 ,也存在类似于联苯衍生物的构型和构象问题 .确定了手性碳原子的构型 ,还必须确定两个芳环间的构型和构象 .运用笔者提出的螺旋理论 ,通过其旋光方向和旋光度可以方便地确定秋水仙碱两个芳环间的构型和构象 . 相似文献
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We classify gapped topological superconducting (TSC) phases of one-dimensional quantum wires with local magnetic symmetries, in which the time-reversal symmetry is broken, but its combinations with certain crystalline symmetries, such as , , and , are preserved. Our results demonstrate that an equivalent BDI class TSC can be realized in the or superconducting wire, which is characterized by a chiral Zc invariant. More interestingly, we also find two types of totally new TSC phases in the and superinducting wires, which are beyond the known AZ class, and are characterized by a helical Zh invariant and Zh⊕Zc invariants, respectively. In the Zh TSC phase, Z pairs of Majorana zero modes (MZMs) are protected at each end. In the case, the MZMs can be either chiral or helical, and even helical-chiral coexisting. The minimal models preserving or symmetry are presented to illustrate their novel TSC properties and MZMs. 相似文献