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

铟-过渡金属组合试剂高效合成有机反应的发展

基本信息

批准号：
14340195
负责人：
ARAKI Shuki
金额：
$ 9.15万
依托单位：
Nagoya 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 2005
项目状态：
已结题

项目摘要

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.

为了开发新的合成反应和新型的功能群转换，有机嵌入化合物和过渡金属复合物（例如镍和钯化合物）组合的合成效用。该项目中获得的结果可以概括如下。1.π-酰胺醛配合物已通过减少鉴定（i）碘化物的变化来轻松地转换为Allic依赖试剂。该反应也可以应用于相应的π-甲基尼克络合物，并且可以使用多种种类的种植物质，包括近种醇本身，而无需任何激活。由π-甲列帕拉德宫和π-乙乙基岩体制备的种植型试剂显示出略有不同的行为。此处开发的方法提供了一种新颖且有用的环境良性过程。2。三元环化合物（例如环丙烯，环氧化物和阿苏里线）的反应，并系统地研究了Allic鉴定试剂。这些反应提供了各种类型的产品，包括一些重排的化合物。研究了它们的反应机制，并讨论了区域和立体选择性。3。在拳头的时间里，已经发现了通过近叶鉴定试剂的光解会产生的拳头。分子内环化反应以高屈服后，提供各种碳循环。和杂环化合物。详细研究了配体对依赖性和反应溶液的反应机理和反应溶液的作用。4。研究了甘油化合物的合成使用，这是第13组元素的另一个成员，并且已经讨论了它们与相应鉴别化合物的反应性和反应行为的相似性。

项目成果

期刊论文数量（17）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Stereoselective allylation of azirines with allylindium reagents

DOI：
10.1016/j.tetlet.2005.12.119
发表时间：
2006-03
期刊：
Tetrahedron Letters
影响因子：
1.8
作者：
T. Hirashita;Shinya Toumatsu;Y. Imagawa;S. Araki;J. Setsune
通讯作者：
T. Hirashita;Shinya Toumatsu;Y. Imagawa;S. Araki;J. Setsune

Indium and Gallium, Comprehensive Organometallic Chemistry III

铟和镓，综合有机金属化学 III

DOI：
发表时间：
2006
期刊：
影响因子：
0
作者：
T.Hirashita;K.Mitsui;Y.Hayashi;S.Araki;S.Araki et al.;T.Hirashita et al.;S.Araki;S.Araki et al.
通讯作者：
S.Araki et al.

Photochemical and Radical Initiator-induced Reaction of Allylic Indium Compounds

烯丙基铟化合物的光化学和自由基引发剂诱导的反应

DOI：
发表时间：
2005
期刊：
Tetrahedron Lett. 46
影响因子：
0
作者：
S.Araki;T.Hirashita;T.Hirashita et al.;T.Hirashita et al.;T.Hirashita et al.;T.Hirashita
通讯作者：
T.Hirashita

Nickel-catalyzed indium(I)-mediated double addition of aldehydes to 1,3-dienes