Development of Highly Efficient Synthetic Organic Reactions with Indium-transition Metal Combined Reagents

为了开发新的合成反应和新的官能团转化，研究了有机铟化合物与过渡金属配合物（如镍和钯化合物）结合的合成用途。本项目取得的成果可以总结如下：1。π-烯丙基钯配合物经碘化铟还原金属转化后，很容易转化为烯丙基铟试剂。该反应也适用于相应的π-烯丙基镍配合物，并且可以使用包括烯丙醇本身在内的各种烯丙基化合物而无需任何活化。由π-烯丙基钯和π-烯丙基镍配合物制备的烯丙基铟试剂表现出略微不同的行为。这里开发的方法提供了一种新颖而有用的无害环境的过程。本文系统地研究了环丙烯、环氧化物、氮嘧啶等三元环化合物与烯丙基铟试剂的反应。这些反应产生各种各样的产物，包括一些重排的化合物。研究了它们的反应机理，讨论了它们的区域选择性和立体选择性。首次发现烯丙基铟试剂光解容易产生烯丙基自由基。分子内环化反应以高收率生成各种碳环和杂环化合物。详细研究了反应机理以及配体对铟和反应溶剂的影响。研究了13族元素中镓化合物的合成用途，并讨论了它们与铟化合物在反应活性和反应行为上的相似性。

The synthetic utility of the combination of organoindium compounds and transition-metal complexes, such as nickel and palladium compounds, has been studied in order to develop new synthetic reactions and novel functional group transformations. The results obtained in this project can be summarized as follows.1.π-Allylpalladium complexes have been found to be converted readily to allylic indium reagents by the reductive transmetallation with indium(I) iodide. This reaction can be applied also for the corresponding π-allylnickel complexes, and a variety of allylic compounds including allylic alcohol themselves can be used without any activation. The allylic indium reagents prepared from π-allylpalladium and π-allylnickel complexes showed slightly different behavior. The methodology developed here provides a novel and useful environmentally benign process.2.The reactions of three-membered ring compounds, such as cyclopropenes, epoxides, and azirines, with allylic indium reagents have been systematically studied. These reactions gave a various type of products including some rearranged compounds. Their reaction mechanisms were investigated and the regio- and stereoselectivity were discussed.3.Allylic radicals have been found for the fist time to be generated easily by the photolysis of allylic indium reagents. Intramolecular cyclization reactions follow in high yields to furnish various carbocyclic and heterocyclic compounds. The reaction mechanism and the effects of the ligands on indium and the reaction solvents were investigated in detail.4.The synthetic use of gallium compounds, another member of the group 13 elements, has been investigated and their similarity in the reactivity and reaction behavior to the corresponding indium compounds has been discussed.