Generation of Transition Metal-Containing 1,3-Dipoles and their Application for the Synthesis of Cyclic Compounds

本研究主要探讨含过渡金属的1，3-偶极分子的产生及其在多环化合物合成中的应用。当邻炔基苯基羰基衍生物与催化量的W（CO）_5（thf）作用时，羰基氧在亲电活化的炔上发生6-内模式环化反应，生成含钨羰基叶立德，其与富电子烯烃通过[3+2]-环加成反应生成含氧多环化合物，然后通过分子内C-H插入所产生的不稳定的卡宾络合物中间体。在三乙基硅烷存在下，这些含钨卡宾中间体被三乙基硅烷顺利地捕获在分子间，生成含硅环加合物，并再生W（CO）5物种;同样地，用W（CO）5（L）处理N-（邻炔基苯基）亚胺衍生物，诱导亚胺氮在亲电活化的炔部分上的5-内模式环化，得到含金属的甲亚胺叶立德。这些叶立德与各种富电子烯烃的[3+2]-环加成反应也顺利进行，得到不稳定的卡宾配合物，这些配合物又发生1，2-氢、烷基、芳基迁移，以良好的产率得到吲哚核3-位上有烷基或芳基取代基的6-5-5三环吲哚骨架。

In this research project, generation of transition metal-containing 1,3-dipoles, novel reactive species, and their application for the synthesis of polycyclic compounds were investigated. When the o-alkynylphenyl carbonyl derivatives were treated with a catalytic amount of W(CO)5(thf), 6-endo-mode of cyclization of the carbonyl oxygen onto the electrophilically-activated alkyne moiety took place to give novel reactive species, tungsten-containing carbonyl ylides, which reacted with electron-rich alkenes to give oxygen-containing polycyclic compounds through [3+2]-cycloaddition reaction followed by intramolecular C-H insertion of the produced non-stabilized carbene complex intermediates. In the presence of triethylsilane, these tungsten-containing carbene intermediates were smoothly trapped intermolecularly by triethylsilane to give silicon-containing cycloadducts with regeneration of the W(CO)5 species.Similarly, treatment of N-(o-alkynylphenyl)imine derivatives with W(CO)5(L) induces the 5-endo-mode of cyclization of the imine nitrogen onto the electrophilically-activated alkyne moiety to afford metal-containing azomethine ylides. [3+2]-cycloaddition of these ylide species with various electron-rich alkenes also proceeded smoothly to give unstable carbene complexes, which in turn undergo 1,2-hydrogen, alkyl, aryl-migration to afford in good yield 6-5-5 tricyclic indole skeletons having an alkyl or an aryl substituent at the 3-position of indole nucleus.