金催化联烯的分子间环加成反应研究

Homogeneous gold catalyzed reactions have been widely explored in recent years. Activation of the alkenes and alkynes by gold catalyst was based on its lewis acidity through Dewar-Chatt-Duncanson type complexation. It was found that the complexation of the auric cation with allene lead to the formation of the Au-C bond containing allylic cation intermediate, the reactivity of which would resemble that of 1, 3-dipoles. Based on this reactivity, a variety of intramolecular cycloaddition reactions have been developed, including [2+2]、[2+3]、[2+4]、[3+4] cycloaddition reactions. Two possible routes were involved, according to the reaction mode of carbon cation intermediate with vinyl gold intermediate. Despite these achievements, there are few examples of gold catalyzed intermolecular cycloaddition reactions of allenes till now. We have reported the intermolecular [2+2] cycloaddition reaction of allenamide with electro-rich olefins via gold catalysis, to provide a series of polysubstituted cyclobutane derivatives. In this project, we will try to develop a new method to synthesize mono- or polycyclic compounds through the gold catalyzed intermolecular cycloaddition reactions of allenes with suitable reactants

金催化剂对烯烃、炔烃的催化反应基于其Lewis酸性质，通过与不饱和键发生Dewar-Chatt-Duncanson模式配位，从而活化不饱和键。其与联烯的配位会形成含碳金键的烯丙基正离子中间体，同时含有电正性和电负性的碳原子，具有偶极子的反应特性。根据这一性质，人们发展了多种类型的金催化联烯的分子内环加成反应，包括[2+2]、[2+3]、[2+4]、[3+4]环加成反应过程。其中，根据中间体碳正离子与烯基金反应位点的不同，可以分为两种类型的反应路径。但是，有关金催化联烯的分子间环加成反应的报道很少。本课题将着眼于这一问题，在现有的研究基础上（金催化联烯胺与富电子烯烃的分子间[2+2]环加成反应生成环丁烷衍生物），发展出一类高效、高选择性的单环或多环合成方法。

金催化剂与联烯的配位会形成含碳金键的烯丙基正离子中间体，同时含有电正性和电负性的碳原子，具有偶极子的反应特性。根据这一性质，人们发展了多种类型的金催化联烯的分子内环加成反应，包括[2+2]、[2+3]、[2+4]、[3+4]环加成反应过程。.本课题着眼于发展金催化联烯的分子间环加成反应过程，与分子内反应过程相比，分子间反应过程的区域选择性会存在一定的问题。面对这一问题，我们通过采用特殊的底物类型-联烯胺衍生物来解决。.在课题申报之前，本课题组已经报道了金催化联烯胺与富电子烯烃的分子间[2+2]环加成反应合成生成环丁烷衍生物的方法。项目批准了以后，我们主要发展了两种类型的环化反应，.1，发展了金催化联烯与硝酮分子间【2+3】环加成反应, 金催化联烯与Azomethine Imine等化合物的分子间【2+3】环加成反应；以及联烯与色胺衍生物的加成环化反应。.2，用银催化剂替代金催化剂，发展了银催化的重氮酯与醛的【2+1】环加成反应及银催化重氮酯与醛和烯/炔等化合物的【2+2+1】环加成反应。