聚铝氨烷－钌－镧对1－己烯醛化反应的催化作用

聚铝氨烷－钌－镧对１－己烯醛化反应的催化作用杨荣华，吴晓龙，黄美玉，江英彦（黑龙江大学化学系哈尔滨１５００８０）（黑龙江省科学技术协会哈尔滨）（中国科学院化学研究所北京）关键词高分子催化剂，己烯，醛化，聚铝氨烷－钌－镧配合物醛化反应通常以羰基铑、羰基...     

1，1′－联萘－2，2′－二胺的合成及在不对称合成中的应用

综述了1，1′－联萘－2，2′－二胺（联萘胺）化合物的制备，讨论了它们作 为手性辅助基或配体在烯烃、酮、亚胺的不对称氢化及在烯烃的不对称环丙烷化、 醛的烷基化反应、醛的不对称烯丙基化反应、不对称烯丙位取代反应和不对称 Diels-Alder反应等反应中的应用。     

(1R,2S)或(1S,2R)-1,2-二苯基-2-氨基乙醇衍生物手性配体的合成及其用于不对称催化反应

重点报道了以（１Ｒ，２Ｓ）或（１Ｓ，２Ｒ）－１，２－二苯基－２－氨基乙醇衍生物手性配体的合成及其用于不对称催化反应的研究，如去氢氨基酸的氢化、醛的乙基锌加成、酮的还原、活泼亚甲基化合物的烷基化、醛的硅腈化和瑞福马斯基反应等．研究了手性配体的结构、底物和反应条件等对上述反应的对映选择性和催化活性的影响．     

氯铝酸室温离子液体中缩醛和缩酮反应

以取代硫酸等无机酸，实现清洁合成为目的，在1－烷基吡啶和1－甲基－3－ 烷基咪唑季胺盐与无水AlCl_3构成的室温离子液体为催化剂和反应介质中，尝试了 醛和酮与甲醇的缩合反应。醛与甲醇反应，产物以缩醛为主，酮与甲醇反应则有相 当量的Aldol缩合产物。依反应底物不同，可获得中至高的转化率和选择性。同时 ，一些产物因不溶于离子液体中而分层，便于产物分离。     

双中心协同催化作用在不对称合成中的应用

介绍了双中心协同催化作用的概念以及A型和B型两类催化剂。综述了A型催化 剂在不对称硝基－类羟醛反应、迈克尔加成反应、亚胺和醛的氢膦酰化反应、曼尼 希反应、不对称醛酮羟醛反应以及环氧开环反应中的应用；同时简要介绍了B型催 化剂在不对称合成中的应用。     

应用微波辐射技术一步合成4－芳基－1，4－二氢吡啶衍生物

以芳醛、乙酰乙酸乙酯、醋酸铵为原料在无溶剂条件下应用微波技术合成了4 －芳基－2，6－二甲基－3－5－二乙氧羰基－1，4－二氢吡啶，该反应的2－5min 内完成，产率73％－99％。     

水溶性钯配合物催化柠檬醛的选择加氢反应研究 Ⅰ.反应条件的影响

研究了在水／有机物两相体系中水溶性钯－膦配合物催化柠檬醛的加氢反应．考察了反应温度、氢气压力、底物和催化剂浓度、反应时间、水相ｐＨ值等对该反应的影响，并与几种柠檬醛衍生物的加氢结果进行了比较．发现仅用蒸馏水作水相，则主要产物是二氢香茅醛（＞９３％）；而水相中加入Ｎａ２ＣＯ３后，则主要产物为香茅醛（９７％），且加氢速度比同样条件下使用Ｐｄ／Ｃ催化剂快得多．     

N—芳基—α—氨基苄基膦酸的合成及对钢铁的缓蚀性能研究

Ｎ－芳基－α－氨基苄基膦酸的合成及对钢铁的缓蚀性能研究朱传方高新蕾肖海燕（华中师范大学化学系武汉４３００７０）用于金属螯合和缓蚀的含氮烃基膦酸主要是应用甲醛、胺、亚磷酸酯（或亚磷酸）通过Ｍａｎｎｉｃｈ反应得到［１，２］而应用其它的醛尤其芳醛与胺合成膦...     

（1R,2S）或（1S,2R）—1,2—二苯基—2—氨基乙醇衍生物手性配体的合成及其用于不

重点报道了以（１Ｒ，２Ｓ）或（１Ｓ，２Ｒ）－１，２－二苯基－２－氨基乙醇衍生物手笥配体的合成及其用于不对称催化反应的研究，如去氢氨基酸的氢化，醛的乙基锌加成，酮的还原，活泼亚甲基化合物的烷基化，醛的硅腈化和瑞福马斯基反应等。研究了手性配体的结构，底物和反件等对上述反应的对映造反性和催化活性的影响。     

高立体选择性合成及鉴定(9E,11E)-十四碳二烯-1-乙酸酯(淡褐苹果蛾性信息素)

根据Schlosser-Wittig反应，采用溴代ω－羟基壬烷基三苯基膦盐与2E－戊烯醛反应，产物经进一步酯化生成淡褐苹果蛾性信息素－（9E，11E）－十四碳二烯－1－乙烯酯，产物中（9E，11E）异构体含量可达98％。     

Competitive thermal ene reaction and Diels-Alder reactions of 2-[N-(alk-2-enyl)benzylamino]-3-vinylpyrido[1,2-a]pyrimidin-4(4H)-ones

Thermal reaction of 2-[N-(alk-2-enyl)benzylamino]-3-(2-substituted and 2,2-disubstituted)vinylpyrido[1,2-a]pyrimidin-4(4H)-ones gave azepine, the desired ene products, and/or pyran derivatives. The formation of the latter was responsible for the [4+2] cycloaddition reaction between the α,β-unsaturated ester carbonyl moiety as a diene part and the alkenylamino moiety as an ene one. The reaction features depended upon the kinds of substituents both on the vinyl and alkenyl counterparts; strongly electron-withdrawing substituents on the vinyl moiety or an electron-donating substituent on the alkenyl one changed the reaction feature from the ene reaction to the hetero Diels-Alder reaction.     

钯催化的交叉偶联反应——2010年诺贝尔化学奖获奖工作介绍

钯催化的交叉偶联反应是非常实用的合成新方法.文章给出了Heck反应、Negishi反应和Suzuki反应的概念,对其反应机理作了详细的说明,并对其在复杂化合物和天然产物全合成中的应用作了评价.     

基本化学反应形式的系统分类

The old classification of basic chemical reactions was evaluated and a new systematic classification of basic reactions was proposed.In the new classification,all the chemical reactions were divided into oxidation-reduction reactions and non-oxidation-reduction reactions,and both can be divided into combination reaction,decomposition reaction and replacement reaction,respectively.In addition,a new class of basic reactions,the complicated decomposition reaction,was appended to reaction system.     

A rapid and convenient synthesis of 5-unsubstituted 3,4-dihydropyrimidin-2-ones and thiones

A rapid and convenient synthesis of 5-unsubstituted 3,4-dihydropyrimidin-2-ones and thiones was developed. The reaction involves a one-pot reaction between oxalacetic acid, thiourea/urea, and aldehyde under microwave irradiation and provides the products in good yields and much shorter reaction times.     

Ni催化的碳(sp2)-碳和碳(sp2)-杂交叉偶联反应

综述了Ni催化的碳(sp²)-碳和碳(sp²)-杂交叉偶联反应. 主要反应类型有: Heck反应、Sonogashira反应、Kumada-Corriu反应、Negishi反应、Stille反应、Suzuki反应、Ullmann反应、C—N偶联反应、C—O偶联反应、C—P偶联反应和C—S偶联反应. 详细地介绍了各个反应的底物要求、反应条件、反应选择性和产率. 最后, 我们对Ni催化的反应机理研究也作了总结.     

有机化学反应中间体的质谱分析

有机化学反应中活性中间体的性质各异,对反应中间体的表征和研究对于阐明和确证反应机理、优化反应条件、筛选催化剂和发现新类型反应至关重要.近年来,质谱技术和在线微量采样技术的发展,极大程度地拓展了质谱学在该领域的应用.本文总结了近年来本领域发展的新策略、技术和方法,以及有机质谱技术在反应中间体研究中的应用.     

Current progress of molybdenum carbide-based materials for electrocatalysis: potential electrocatalysts with diverse applications

Electrocatalysts are the cores of many electrochemical reactions including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), nitrogen reduction reaction (NRR), and CO₂ reduction reaction (CO₂RR). Recent advances in research have demonstrated the potentials of molybdenum carbide-based catalysts for these reactions arising out of their unique electronic structure and physicochemical properties. In this review, we systematically summarize the recent advances of molybdenum carbide-based catalysts in these electrochemical processes. The corresponding synthesis strategies, structure and electrocatalytic performance of the catalysts are discussed and the relationships of the process-structure-property are highlighted. In addition, the catalytic mechanisms are analyzed based on the structure characterization and theoretical calculations results. Finally, the existing challenges and future perspectives are put forward for further development of molybdenum carbide-based catalysts.     

Photoinduced Atom Transfer Radical Addition/Cyclization Reaction between Alkynes or Alkenes with Unsaturated α-Halogenated Carbonyls

We have developed a photochemical ATRA/ATRC reaction that is mediated by halogen bonding interactions. This reaction is caused by the reaction of malonic acid ester derivatives containing bromine or iodine with unsaturated compounds such as alkenes and alkynes in the presence of diisopropylethylamine under visible light irradiation. As a result of various control experiments, it was found that the formation of complexes between amines and halogens by halogen-bonding interaction occurs in the reaction system, followed by the cleavage of the carbon–halogen bonds by visible light, resulting in the formation of carbon radicals. In this reaction, a variety of substrates can be used, and the products, cyclopentenes and cyclopentanes, were obtained by intermolecular addition and intramolecular cyclization.     

Variable Time Normalization Analysis: General Graphical Elucidation of Reaction Orders from Concentration Profiles

The recent technological evolution of reaction monitoring techniques has not been paralleled by the development of modern kinetic analyses. The analyses currently used disregard part of the data acquired, thus requiring an increased number of experiments to obtain sufficient kinetic information for a given chemical reaction. Herein, we present a simple graphical analysis method that takes advantage of the data‐rich results provided by modern reaction monitoring tools. This analysis uses a variable normalization of the time scale to enable the visual comparison of entire concentration reaction profiles. As a result, the order in each component of the reaction, as well as k_obs , is determined with just a few experiments using a simple and quick mathematical data treatment. This analysis facilitates the rapid extraction of relevant kinetic information and will be a valuable tool for the study of reaction mechanisms.     

糖碳苷类化合物的合成方法研究进展

综述了近年来利用重排反应、W ittig反应、金属有机反应等方法合成糖碳苷类化合物的研究进展。参考文献30篇。