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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.

可以开发新型的铟试剂并应用于有机合成。进行以下反应。（1）氢化铟的产生及其在还原各种官能团中的应用。（2）氯化铟和氢化硅烷生成新型刘易斯酸体系：作为方法1的一个例子，氯化二氯化铟（Cl_2InH）可以通过三丁基氢化锡和InCl_3之间的金属交换反应生成。由于氢化铟难以世代相传，因此很少用于有机合成。这是铟氢化物在有机合成中的首次应用。生成的Cl_2InH可还原醛、酮、酰氯和烷基卤化物等多种官能团。特别地，酰基卤的还原得到作为唯一产物的H2O。烯丙基铟也可取代铟的取代物，与酰氯反应，选择性地生成高烯丙基酮。在这些反应中，氧化膦作为配体对铟试剂的反应活性起着重要的控制作用。氢化铟能有效地还原自由基反应中的卤代烷。特别是室温自由基反应可以实现。其次，作为方法2的一个例子，氯化铟通过与氢硅烷结合而充当一种新型的刘易斯酸。芳香族化合物与羰基化合物之间的还原Friedel-Crafts反应得以实现。In-Si体系能使酮脱氧生成烷烃。该方法可以扩大到以脱氧方式将各种官能团引入酮。此外，还可以建立醇类的脱氧方法，适用于各种醇类，包括芳香族和脂肪族醇类。