NiSO_4／γ－Al_2O_3对低级烯烃齐聚反应的催化作用

用ＮａＯＨ和ＣＯ中毒法、ＥＳＲ检测等方法研究了ＮｉＳＯ４／γ－Ａｌ２Ｏ３催化剂上乙烯、丙烯和１－丁烯齐聚反应的催化作用．结果表明：催化剂的酸性对烯烃的齐聚反应起重要作用，并且反应活性主要与Ｈｏ－３．０的酸中心有关，乙烯二聚反应是通过配位催化进行的，其活性中心是Ｎｉ＋，丙烯齐聚是通过Ｎｉ＋上的配位催化和酸催化进行的，而１－丁烯齐聚则是通过酸催化机理进行     

手性纯的4,4-二苯基取代的末端环氧化合物的合成

烷基锂先与1,1-二苯乙烯反应生成相应的1,1-二苯烷基锂, 接着在－70 ℃下滴加手性环氧氯丙烷, 然后回到室温搅拌几小时, 按常法处理后, 得到手性纯的4,4-二苯基取代末端环氧化合物, 它们的ee值均大于90%, 此外还对反应机理进行了讨论. 通过元素分析及NMR对产物的结构进行了表征.     

In an attempt to provide a user's guide to the galaxy of benzylidene, alkoxybenzylidene, and indenylidene ruthenium olefin metathesis catalysts

The data reported in this paper demonstrate that great care must be taken when choosing an appropriate catalyst for a given metathesis reaction. First-generation catalysts were found to be useful in the metathesis of sterically unhindered substrates. Second-generation catalysts (under optimised conditions) showed good to excellent activities toward sterically hindered and electron-withdrawing group (EWG)-substituted alkenes that do not react using the first-generation complexes. A strong temperature effect was noted on all of the reactions tested. Interestingly, attempts to force a reaction by increasing the catalyst loading were much less effective. Therefore, when possible, it is suggested that metathesis transformations should be carried out with a second-generation catalyst at 70 degrees C in toluene. However, different second-generation catalysts proved to be optimal for different applications and no single catalyst outperformed all others in all cases. Nevertheless, some empirical rules can be deduced from the model experiments, providing preliminary hints for the selection of the optimal catalysts.     

NHC-Palladium-Catalyzed Cascade Annulation of Alkynoic Acids with Unactivated Alkenes in Ionic Liquids

An N-heterocyclic carbene palladium (NHC-palladium)-catalyzed cascade annulation of alkynoic acids with unactivated alkenes under an oxygen atmosphere in ionic liquids is described. This protocol enables facile access for the preparation of diverse alkyl substituted α-methylene-γ-lactones in moderate to good yields with excellent Z/E selectivity. Moreover, the ionic liquid not only acts as the green solvent, but also as the eco-friendly chlorine source, thus avoiding the use of excess metal halides such as cupric chloride. Some preliminary mechanistic studies were performed, which further revealed possible pathways for this cascade annulation.     

Oxidative Dehydrogenation of Alkanes through Homogeneous Base Metal Catalysis

Preparing valuable olefins from cheap and abundant alkane resources has long been a challenging task in organic synthesis, which mainly suffers from harsh reaction conditions and narrow scopes. Homogeneous transition metals catalyzed dehydrogenation of alkanes has attracted much attention for its excellent catalytic activities under relatively milder conditions. Among them, base metal catalyzed oxidative alkane dehydrogenation has emerged as a viable strategy for olefin synthesis for its usage of cheap catalysts, compatibility with various functional groups, and low reaction temperature. In this review, we discuss recent development of base metal catalyzed alkane dehydrogenation under oxidative conditions and their application in constructing complex molecules.     

Study on the 1,3-dipolar cycloaddition reaction of 4-ethoxy-1,1,1-trifluoro-3-buten-2-one with nitrile oxides

1,3-Dipolar cycloaddition (1,3-DC) reaction of 4-ethoxy-1,1,1-trifluoro-3-buten-2-one 1 with nitrile oxides was studied. It was found that besides its CC participating in the formation of isoxazole rings, trifluoromethyl activated CO also underwent 1,3-DC reaction with nitrile oxides to afford 1,4,2-dioxazole rings. Single crystal diffraction analysis also evidenced the diheterocyclic configuration.     

手性双官能硫族化合物催化烯烃的不对称亲电硫化反应

手性含硫化合物在药物化学和不对称合成领域中应用广泛,发展这类化合物的新合成方法是有机合成化学的重要任务.烯烃的不对称亲电硫化反应为手性含硫化合物的合成提供了一条方便的途径,通过这种方式不仅可以在烯烃母体分子上引入一个含硫基团,同时也能够引入另外一个重要的官能团.我们课题组设计、合成了一系列手性双官能硒醚/硫醚催化剂,并成功将其应用在不同种类烯烃的分子内和分子间的不对称三氟甲硫基化、烷硫基化和芳硫基化反应,高对映选择性地合成了各种手性含硫化合物.总结了我们课题组在手性双官能硒醚/硫醚催化的烯烃不对称亲电硫化反应中的研究进展,并对该领域的发展进行展望.     

钯催化的1,4-环己二烯的立体选择性1,3-双芳基化反应

基于金属迁移的策略,发展了钯催化的1,4-环己二烯的1,3-双芳基化反应,得到单一的非对映选择性的双芳基化的产物.此反应具有优秀的区域选择性和单一的非对映选择性.实验结果表明在钯迁移的过程中烯烃并没有从钯上解离下来.这一研究为cis-1,3-双芳基取代的环己烷类化合物的合成提供了简便的方法.     

A selective and cost-effective method for the reductive deuteration of activated alkenes

A new single electron transfer reaction for the reductive deuteration of activated alkenes has been developed for the selective synthesis of α,β-dideuterio compounds. A cheap, stable and commercially-available sodium dispersion with high specific surface area is employed as the electron donor to replace the traditionally used sodium/liquid ammonium system. Deuterium source is provided by EtOD-d₁. Excellent yields and deuterium incorporations were obtained across a broad range of activated alkenes with good functional group tolerance. This method provided a cheap, efficient and operationally-simple method for the synthesis of deuterium labeled compounds.