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

含过渡金属1,3-偶极子的生成及其在环状化合物合成中的应用

基本信息

批准号：
14340194
负责人：
KUSAMA Hiroyuki
金额：
$ 6.66万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14340194/
关键词：
Tungsten 1,3-Dipolar Cycloaddition carbene Complex Indole 1, 3- 双極子 1, 5- 双極子 3+2 付加環化 5+2 付加環化カルボニルイリド塩化白金ナフタレンアゾメチンイリド [3+2]付加環化反応

项目摘要

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.

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。在三乙基硅烷的存在下，这些含钨卡宾中间体被三乙基硅烷顺利地捕获在分子间，并再生W（CO）5物种，得到含硅环加合物。同样，用W（CO）5（L）处理N-（邻炔基苯基）亚胺衍生物，诱导了5-内模式的环化，将亚胺氮环合到亲电活化的炔部分上，得到含金属的偶氮甲碱叶立德。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。