Generation of Active Indium Reagent from

生成活性铟试剂

基本信息

批准号：
11650874
负责人：
BABA Akio
金额：
$ 2.24万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650874/
关键词：
Indiuum compounds Reduction Tin Hydride Radical Reaction Hydrppsilane Lewis Acid Alcohol Deoxygnation インジウム還元脱ハライド Friedel-Crafts 脱酸素

项目摘要

Novel type of indium reagents could be developed and were applied to organic synthesis. Following reactions were performed. (1)Generation of indium hydride and its application to the reduction of various functionalities. (2)Novel Lewis acid system generated by indium chloride and hydrosilanes.As a example of method 1, dichloroindium chloride(Cl_2InH)could be generated by transmetallation between tributyltin hydride and InCl_3. Indoium hydride have scarcely been used in organic synthesis because of difficulty to their generations. This is the first application of injium hydride in organic synthesis. The generated Cl_2InH could reduce various functional group such as akdehydes, ketones acid chloride and alkyl hakides. In particular, the reduction of acid halide gave an aldehyd as a sole product. In place of indium hydrie, allylic indium also could be generated, which react with acid chloride to give homoallyl ketones selectively. In these reaction, phosphine oxide played an important role as a ligand to control the reactvity of indium reagent. Indium hydride could reduce alkyl halide effectively where the reaction involved radical process. In particular, room temperature radical reacttion could be attained. In addition the use of indium hydride underwent radical cyclization reactions.Secondary, as a example of method 2, indium chloride acted as a novel Lewis acid by the combination with hydrosilanes. Thus reductive Friedel-Crafts reaction between aromatis and carbonyl compounds were performed. The In-Si system enable the deoxygenation of ketones to give alkanes. This method could be enlarged to introduce various functionalities to ketones in deoxygenatice manner. Moreover, deoxygenarion of alcohols could be established.where various alcohols including aromatic and aliphatic ones could be applicable.

可以开发新型的依赖试剂并将其应用于有机合成。进行以下反应。（1）氢化酰胺的产生及其用于降低各种功能的应用。（2）通过氯化二氯化物和氢硅烷产生的新型刘易斯酸系统。作为方法1的一个例子，可以通过氢化物和含有二氯二氯化二氯内二氯化物（CL_2INH）产生。氢化物几乎没有用于有机合成，因为它们的世代难度。这是Hydride在有机合成中的第一次应用。生成的CL_2INH可以减少各种功能组，例如Akdehydes，酮酸氯化物和烷基Hakides。特别是，酸卤化物的还原产生了醛作为唯一产物。还可以代替二氢蛋白，也可以产生烯丙基依赖性，与氯化物反应以选择性地给予同甲基酮。在这些反应中，氧化磷作为配体的重要作用，可以控制依赖剂试剂的反应。氢化物可以在反应涉及自由基过程的情况下有效地降低卤化物。特别是，可以实现室温自由基反应。此外，氢化酰胺的使用也经历了自由基环化反应。作为方法2的示例，氯化二氮用与水硅烷的结合充当了新型刘易斯酸。因此，进行了芳香族和羰基化合物之间的还原性弗里德尔工艺反应。 IN-SI系统使酮的脱氧能够给出烷烃。可以扩大此方法以Deoxygenatice的方式将各种功能引入酮。此外，可以建立醇的脱氧剂，包括芳香和脂肪族含量在内的各种醇。