信息检索实习报告.doc

作业要求：卷面清楚，可打印或手抄。网 络 资 源 与 信 息 检 索 课综 合 实 习 报 告 一、报告概况1.课题名称：有机催化剂的合成和应用 2.检索人员：王雅鑫 学号:0413021373.反映课题内容的关键词以及相似词、同义词中英文关键词(3-5个中英文): 有机催化剂 有机催化剂的合成 有机催化剂的应用 organic catalysts The synthesis of organic catalysts The application of organic catalysts 4.中图法类号、类目: (/)类号：O621.3类目：数理科学和化学化学有机化学有机化学一般性问题有机合成化学 5.简要分析课题的主题内容：新型有机催化剂的合成及应用属于化学类学科，此课题首先对新型有机催化剂有个系统的了解，特别是它的性质及其应用和发展前景。然后根据以上资料资源，了解了新型有机催化剂在国内外前沿的制备方法，分析各种方法的利弊。最后对新型有机催化剂的应用及前景做了展望。二、课题检索报告（一）、图书1、通过数字图书馆或图书馆查找与你课题相关的图书，记下一本图书的书名、作者、出版发行项、浏览书中与课题相关的章节并简述该书的主要内容。书名：中德金属有机催化剂和烯烃聚合进展作者：JunquanSun，ChristophJaniak编【出版项】 北京：化学工业出版社 , 2001【ISBN号】7-5025-3465-2【中图法分类号】TQ426.8-53;TQ221.21-53主要内容：本书汇编了中德金属有机催化剂和烯烃聚合反应进展研讨会的德国、日本、中国等国际知名学者的25篇论文，内容涉及近年来茂金属催化剂及有机硼助催化剂的合成、分析和表征；乙烯、丙烯、苯乙烯以及极性单体等在茂金属催化剂的作用下的聚合反应两个方面。（二）、 网页信息搜索（利用引擎的网页搜索查找与课题相关的文章）搜索引擎名称及网址：百度 检索表达式与检索过程：检 索 表 达 式：（主题=有机催化剂）and（主题=合成方法）and（主题=应用）检索过程：打开百度高级搜索，设置搜索结果包含全部关键词“有机催化剂”并且包含以下任意一个关键词“合成方法”和“应用”设置搜索网页格式是所有格式并且查询关键词仅位于网页标题中，然后进行检索。 检索结果：检出篇数；约475,000个拷贝与课题最相关论文的篇名；(不超过10条记录)a.金属有机化合物在催化不对称合成中的应用-四川理工学院学报(.b.有机催化剂的设计与合成及其在催化黄烷酮类化合物合成中的应用.c. 有机催化及均相金催化策略在新型潜香物质合成中的应用.复旦大学d. 金属有机化合物在催化不对称合成中的应用-【维普网】-仓储式在线.记录一篇与课题密切相关的文献（题名、作者及文献来源）；题名：金属有机化合物在催化不对称合成中的应用作者：谢斌冯建申邹立科张秀兰文献来源：中文科技期刊数据库依据的结果查哪些学校有收藏及收藏地址、借阅状态。纸本收藏：四川理工学院（其他学校无收藏）收藏地址：四川理工学院图书馆借阅状态：在架可借（三）、全文数据库检索（查找与你课题相关的信息）数据库名称：中国学术期刊全文数据库检索年代： 2013-2014检 索 表 达 式：（主题=有机催化剂）and（主题=合成方法）and（主题=应用）检索结果：命中记录数目；53记录三篇与课题密切相关的文献（题名、作者、关键词及文献来源）； a.题名：含氟吡咯-硫脲有机催化剂促进硫醚的选择性氧化过程 作者：谢婷； 陈文华； 李智利 关键词：有机催化剂； 选择性氧化； 硫醚； 氟固相萃取 文献来源：化学试剂 ,Chemical Reagents , 编辑部邮箱 ,2013年03期b.题名：负载有机膦的合成及其在有机催化领域的应用 作者：刘海灵 关键词：负载有机膦； 合成； 有机催化； 有机反应； 文献来源：化学进展 ,Progress in Chemistry , 编辑部邮箱 ,2013年Z1期c.题名：有机催化法烟气脱硫技术在泰钢烧结机上的应用 作者：邵书东； 吴茂林； 赵树民； 关键词：烧结烟气； 脱硫技术； 有机催化法； 二氧化硫； 催化剂 文献来源：山东冶金 ,Shandong Metallurgy , 编辑部邮箱 ,2013年02期 依据中的其中一条结果，阅读全文并利用功能按钮复制粘贴该篇的摘要部分。题名：负载有机膦的合成及其在有机催化领域的应用摘要：有机膦是一类重要的有机催化剂,作为一种亲核催化剂已得到广泛的应用。小分子叔膦作为一种均相催化剂影响产物的分离和催化剂的回收,将膦负载可以弥补上述缺陷。负载叔膦作为一类有机催化剂在近几年才受到关注。本文简要介绍了不同载体负载叔膦的合成方法及应用,综述了其催化Baylis-Hillman、加成、炔酮异构化和羟基保护反应的研究进展,并对研究前景进行了展望。 更多还原【Abstract】 Phosphines are widely used in organic chemistry as nucleophilic catalysts.The employed phosphines are generally homogeneous,which make the separation of products and recovery of catalysts difficult.To overcome these limitations,heterogeneous supported phosphines as organocatalysts have gradually appeared and have been successfully applied in Baylis-Hillman raction,nucleophilic addition reaction,isomerization of ynones,and hydroxyl protection rection.In this article,the progress on synthesis and organocatalysis of supported phosphine with different grafts is reviewed.The outlook of the research area is provided. 更多还原 （四）、学位论文（自选学位论文数据库查找与你课题相关的信息）数据库名称：清华同方中国优秀博士学位论文数据库网址：1/kns55/brief/result.aspx?dbPrefix=CDFD检索年代：2001-2014 检 索 表 达 式：（主题=有机催化剂）and（主题=合成方法）and（主题=应用）检索结果：命中记录数目： 27条 记录一篇与课题密切相关的文献（题名、作者、专业、学位、导师、学校、文摘）题名：新颖有机催化剂的设计、合成及其在C-C形成反应中的应用（Design and Synthesis of Novel Organocatalysts and Their Application for C-C Bond Forming Reactions）作者：郑吉富专业：有机化学学位：博士导师：李耀先； 张锁秦学校：吉林大学文摘： 【中文文摘】 有机小分子催化不对称有机合成(Asymmetric organocatalysis),是连接金属有机催化和酶催化以及合成化学和生物有机化学的桥梁。有机小分子催化剂不含金属离子,对环境友好,且在反应过程中不需要对反应底物进行修饰,符合原子经济性。因而有机小分子催化剂的设计、合成引起了人们的极大关注,并成为现代有机合成化学的前沿领域之一。设计、合成具有高活性、高选择性、并可以循环利用的有机小分子催化剂则是当前研究的热点和前沿。Aldol、nitro-Michael和Henry反应是有机合成中形成C-C键的重要反应。近年来,有机小分子催化剂催化不对称直接aldol和nitro-Michael反应成为人们关注的热点。以天然的手性氨基酸为原料,经保护、酰胺化、脱水、环化、缩和以及脱保护等7步反应合成出3个末端带四唑基团的二肽衍生物,又以邻苯二胺为原料,经环化、缩和、脱保护等3步反应合成出2个末端带苯并咪唑基团的二肽衍生物,并对其合成条件和方法进行了探讨研究。在大量合成实验的基础上,归纳总结二肽衍生物的合成条件和方法,为新颖有机小分子催化剂的进一步合成奠定了基础。将上述二肽衍生物,用于催化酮与芳香醛的不对称直接aldol反应,并详细地考察了反应温度、溶剂、催化剂用量、添加剂等因素对反应活性和对映选择性的影响。研究结果表明:催化剂表现出较好的催化活性和对映选择性。在优化的反应条件下,aldol产物的产率最高达96%,ee值最高可达96%,dr值最高达到97:3。而且,此类催化剂在酮与硝基苯乙烯的nitro-Michael加成反应和硝基甲烷与芳香醛的Henry缩和反应中,也表现出较好的催化活性。 更多还原【Abstract】 Since List et al. demonstrated that L-proline itself could catalyze the intermolecular direct asymmetric aldol reaction, the concept of small organic molecules as catalysts has received considerable attention. In recent few years, asymmetric organocatalysis has matured into a very powerful, practical and broadly applicable third methodological approach in catalytic asymmetric synthesis.Organocatalysts are purely“organic”molecules, i.e. composed of (mainly) carbon, hydrogen, nitrogen, sulfur and phosphorus. As opposed to organic ligands in transition metal complex, the catalytic activity of organocatalysts resides in the low-molecular- weight organic molecule itself, and no transition metals (or other metals) are required. Organocatalysts have several advantages. They are usually robust, inexpensive and readily available, and non-toxic. Because of their inertness toward moisture and oxygen, demanding reaction conditions, for example inert atmosphere, low temperature, absolute solvents, etc., are, in many instances, not required.Recently, many researchers have focused on the design and synthesis of new and highly efficient organocatalysts due to their widely applications in the field of asymmetric synthesis, especially, enantioselective C-C bond forming reactions,such as aldol reaction, Michael reaction, Henry reaction, etc.So we envision that an appropriate incorporating both prolinamide moieties and nitrogen-containing heterocycles in one molecule could give the potential organocatalysts. In this strategy, based on N-terminal prolyl-dipeptides, we replace C-terminal carboxylic acid by tetrazole and benzoimidazole, which can lead to higher the acidity and solubility of catalysts to improve the reactivity and selectivity of the reaction. Five new organocatalysts 1-5 have been prepared.The organocatalysts 1-5 can be readily prepared from N-carbobenzyloxy-L-proline and corresponding-amino acid tetrazole or-aminobenzoimidazole. We seek to use thionyl chloride to chlorinate the N-carbobenzyloxy-L-proline and then reacted without purification with a corresponding-amino acid tetrazole or-aminobenzoimidazole in the suitable solvents to give Cbz-protected products in moderate to good yields (2881%). Finally, hydrogenolysis of the Cbz-protected products in the presence of 5% Pd/C deprotect the N-Cbz group to provide 1-5 in good yield (6380%).The aldol reaction is one of the most important organic reactions, because it is a carbon-carbon bond forming reaction which produces highly functionalized compounds with a pair of newly generated chiral centers. We first examined the ability of the catalysts 1-5 to promote the direct aldol reaction between acetone and 4-nitrobenzaldehyde under various conditions. Catalysts 2 and 5 are identified as the best catalysts for this reaction which lead to aldol adduct with excellent enantioselectivity and ee value up to 96%.The reactions of different aromatic aldehydes with acetone were studied under the optimized conditions (using 10 mol% of 2 as catalyst, in the presence of 10 mol% Et3N). The reactions of different aromatic aldehydes, which bear an electron-withdrawing group on the benzene ring, proceeded smoothly in excellent enantioselectivities (up to 96%) to furnish the aldol adducts. In addition, halogenated benzaldehydes led to decreased yields. Interestingly, the ee values of the products remained at good levels. On the other hand, this catalytic system was proven to be completely ineffective for the aromatic aldehydes with an electron-donating group or without any substitution.The C-terminal carboxylic acid of the dipeptides was replaced with benzimidazole in order to improve the solubility of catalyst and new catalysts 4 and 5 were obtained. Next, using 5 as catalyst, we examined the reactions of different aromatic aldehydes with neat acetone. It was found that catalyst 5 show significant catalytic activity in producing the aldol adducts with good yields and excellent enantioselectivities. Furthermore, compared with catalyst 4, 5 could extend the scope of substrates.Finally, we studied direct aldol reaction of different aromatic aldehydes and cyclic ketone donor catalyzed by catalyst 5. In case of catalyst 5, the reaction was carried out in 6 h at room temperature with cyclopentane to afford the desired products in good yield, up to 96% yield. When cyclohexanone was used as nucleophiles, moderate diasteroselectivities (anti : syn up to 97: 3), enantioselectivities (up to 81% ee) and poor to moderate yields (up to 68% yield) were observed using different aromatic aldehydes.The Michael reaction is also an important C-C bond forming reaction in organic synthesis. So we also investigated the application of catalysts 1-5 for the Michael reaction between ketone and trans-nitrostyrene in different organic solvents at room temperature. In the presence of 10 mol% catalyst loading, catalysts 2, 3 and 5 gave the product of acetone reacting with trans-nitrostyrene in high yield (up to 97% yield), but only in racemic form. Cyclohexanone was also reacted with trans-nitrostyrene in high yield (up to 96% yield) and diastereoselectivity (syn : anti up to 99 : 1), but poor to moderate enantioselectivity (up to 53% ee), in the presence of catalysts 2, 3 and 5.Nitro alcohols are known to have potential utility as useful synthetic intermediates for many organic transformations. Then we extended our studies to Henry reaction. Preliminary results showed that catalysts 4, 5 are able to promote the Henry reaction in high yield (up to 94% yield) at room temperature. However, in all cases no enantioselectivity was observed.Via the researching work of this dissertation, suggest a new strategy in the design of new organocatalysts for direct asymmetric aldol reactions and related reactions and make the design and synthesis of catalyst possible to multiple reactions. （五）、学术会议论文（自选会议论文数据库查找与你课题相关的信息）数据库名称：清华同方中国重要会议论文数据库网址：1/kns55/brief/result.aspx?dbPrefix=CPFD检索年代： 2001.01.01-2014.12.30检 索 表 达 式：（主题=有机催化剂）and（主题=合成方法）and（主题=应用）检索结果：命中记录数目： 6条 记录一篇与课题密切相关的文献（会议名称、时间、地点、届次、论文名称、作者、文摘） 会议名称：中国化学会第26届学术年会不对称催化分会场论文集 时间：2008-07 地点：中国天津 届次：第一届 论文名称：Merrifield树脂接枝二肽:有效可循环使用的有机催化剂用于无溶剂下的不对称Aldol反应（Merrifield Resin-Supported Dipeptides: Efficient and Recyclable Organocatalysts for the Asymmetric Aldol Reactions under Solventless Reaction Conditions） 作者：晏金灿； 魏发钱； 王磊； 文摘：-羟基羰基化合物在合成多官能团化合物和天然产物中是重要的合成砌块,而且-羟基羰基单元具有生物活性,常见于抗菌和抗癌药物中。直接不对称Aldol反应是最直接合成光学活性的有效方法,因而受到化学家的亲睐。尤其是近年来引起人们最为关注的是有机小分子催化剂的设计和在 更多还原（六）、专利文献（自选数据库查找与你课题相关的信息）数据库名称：万方数据之中外专利数据库网址：/C/Patent.aspx检 索 表 达 式：（主题=有机催化剂）and（主题=合成方法）and（主题=应用）检索结果命中记录数目17,864条 记录一篇相关的文献(专利名称、申请号、申请人、发明人、IPC号、专利号、摘要及全文说明书的页数等)。专利名称：一种含有伯胺、叔胺和脲或硫脲的有机催化剂及其制备申请号：CN200810011654.9申请人：中国科学院大连化学物理研究所发明人：梁鑫淼,李鹏飞,叶金星,王永灿IPC号：CN101597286 专利号：CN200810011654.9摘要：本发明涉及有机催化，具体的说是含有伯胺、叔胺和脲或硫脲的有机催化剂及其制备，在一个催化剂分子中，分别含有一个或一个以上的伯胺、一个或一个以上的叔胺、和一个或一个以上的脲或硫脲功能基团。本发明所设计的多功能有机催化剂结构新颖，制备方法简便；因在该类有机催化剂分子中存在伯胺、叔胺和(硫)脲等多个功能基团，在催化不对称有机反应中，能够表现出很好的协同效应，显示出很高的催化效率和光学选择性，能很好地应用于多种类型的有机催化的不对称反应，适用范围广。全文说明书的页数：4页（七）、标准文献（自选数据库查找与你课题相关的信息）数据库名称：万方中外标准数据库网址：/C/Standard.aspx检 索 表 达 式：（主题=有机催化剂）and（主题=合成方法）and（主题=应用）检索结果命中记录数目:11篇记录标准名称、标准号、颁布单位记录标准名称：有机硫加氢催化剂标准号：HG 2505-2004 颁布单位：中华人民共和国国家发展和改革委员会（八）、外文检索工具（自选数据库查找与你课题相关的信息）数据库名称：ACS美国化学学会数据库网址：/检索年限：不限检 索 表 达 式：（关键词=organic catalysts or The synthesis of organic catalysts or The application of organic catalysts）检索结果命中记录数目 19526条记录一条与课题密切相关的信息。标题：Solvent-Adoptable Polymer Ni/NiCo Alloy Nanochains: Highly Active and Versatile Catalysts for Various Organic Reactions in both Aqueous and Nonaqueous Media作者：Manoj Raula , Md. Harunar Rashid , Sima Lai , Mouni Roy , and Tarun K. Mandal *出版日期：2012, 4关键字：polymer; NiCo; alloy; nanochains; catalysts; organic reactions; solvent adoptable摘要：The synthesis of solvent-adoptable monometallic Ni and NiCo alloy nanochains by a one-pot solution phase reduction method in the presence of poly(4-vinylphenol) (PVPh) is demonstrated. The elemental compositions of the as-prepared alloys are determined by inductively coupled plasma optical emission spectroscopy (ICP-OES) and energy-dispersive X-ray spectroscopy (EDS), which are matching well with the target compositions. The morphology analysis by TEM and FESEM confirms that the nanochains are made up of organized spherical monometallic Ni or bimetallic NiCo alloy nanoparticles (NPs). However, there is no nanochain formation when the alloy is prepared without the polymer PVPh. A possible mechanism for the formation of such NiCo alloy nanochains is discussed. The X-ray diffraction and selected area electron diffraction patterns reveal that the Ni/NiCo alloys are polycrystalline with fcc structure. The obtained Ni or NiCo alloy nanostructures are ferromagnetic with very high coercivity. The polymer Ni/NiCo alloy nanochains are dispersible in both water and organic media that makes them versatile enough to use as catalysts in the reactions carried out in both types of media. The catalytic activities of these Ni/NiCo alloy nanochains are extremely high in the borohydride reduction of p-nitrophenol in water. In organic solvents, these nanochains can act as efficient catalysts, under ligand-free condition, for the CS cross-coupling reactions of various aryl iodides and aryl thiols for obtaining the corresponding cross-coupled products in good to excellent yield up to 96%. The NiCo nanochain also successfully catalyzes the CO cross-coupling reaction in organic medium. A possible mechanism for NiCo alloy nanochain-catalyzed cross-coupling reaction is proposed.三、国内外研究概况（综述）1、通过阅读检索到的文献，就国内外对该问题的研究进展与代表观点作一小结（不少于1000字）并明确标注参考文献。自本世纪初,不对称有机催化已经逐渐成为不对称催化领域中一个新的、最具活力的领域。特别是在最近十年中,在新催化剂的设计、新发应的发现和新催化概念的提出方面取得了很大的进展。其中,烯胺催化和氢键催化是有机催化领域中两个重要的催化模式。因此,基于这两个基本活化概念,我们提出了设计具有“可调、多氢键和双功能”特点的有机催化剂的设计思想。根据这一理念,从廉价、易得的L-脯氨酸和光学纯的1,2-环己二胺出发,我们首次设计并合成了一系列新型的结构可调、含多个氢键的双功能二级胺-双酰胺催化剂。 随后,对我们发展的一系列手性二级胺-双酰胺催化剂在环己酮和各种醛的不对称Aldol反应中的催化性能进行了考察。我们发现,这类催化剂表现出了优良的催化活性和选择性的可调性。在最优条件下,反应获得了优异的产率(up to 94%)、非对映选择性(up to 99:1 d.r.)和对映选择性(up to 97%e.e.)。我们进一步研究了这类催化剂催化的水相中的环酮和醛的不对称Aldol反应。实现了以饱和食盐水为反应介质的不对称Aldol反应,同样也获得了很好的非对映选择性(up to 99:1 d.r.)和对映选择性(up to 96%e.e.)。 为了扩展这类新型催化剂的底物普适性,我们进一步研究了其在含杂原子环酮与醛的不对称Aldol反应中的应用。研究表明,这类催化剂同样表现出了优异的催化效能。该催化体系适用于芳香醛,杂芳香醛和脂肪醛,并且对于大多数的底物都以高的产率获得了几乎光学纯的Aldol加成产物(e.e.值高达99%,