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

本课题研究了含过渡金属的1，3-偶极子的生成、新型活性物种及其在多环化合物合成中的应用。用W(CO)5(THF)催化量的W(CO)5(THF)处理邻炔基苯基衍生物时，在亲电活性的炔基上发生6-内环化反应，得到新的活性物种--含钨的羰基叶立德，它与富含电子的烯烃通过[3+2]-环加成反应得到含氧多环化合物，然后生成不稳定的卡宾化合物的分子内C-H插入反应.在三乙基硅烷的存在下，这些含钨的卡宾中间体被三乙基硅烷顺利地捕获到分子间，生成了W(CO)5物种的含硅环加成物。类似地，N-(邻炔基苯基)亚胺衍生物与W(CO)5(L)处理后，亚胺氮以5-内环的方式环合到亲电活性的炔基上，得到了含金属的甲亚胺类化合物。[3+2]这些叶立德物种与各种富电子烯烃的-环加成反应也顺利地进行，得到不稳定的卡宾络合物，这些卡宾络合物依次经历1，2-氢、烷基、芳基迁移，得到在吲哚核的3-位具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.