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Development of Heteroatom Mixed Radical Reaction Systems

杂原子混合自由基反应体系的开发

基本信息

批准号：
13450365
负责人：
OGAWA Akiya
金额：
$ 5.89万
依托单位：
Nara Women's University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

We have developed a series of heteroatom-mixed radical reaction systems, which involve group 15, 16, and 17 heteroatomcompounds. The reactivity of heteroatom radicals toward carbon-carbon unsaturated compounds and carbon-nitrogen unsaturated compounds has been examined in details. As the results, we have found that thio radicals have an excellent reactivity toward these unsaturated compounds, and also that diselenides exhibit an excellent carbon radical capturing ability. Thus, the mixed system of disulfide and diselenide upon photoirradiation conditions provides a useful method for introduction of both thio and seleno groups into a variety of unsaturated compounds such as acetylenes, olefins, allenes, conjugate dienes, vinylcyclopropanes, and isonitrile regioselectively in good yields. This principle can be applied to disulfide-ditelluride mixed system, diselenide-ditelluride mixed system, perfluoroalkyl iodide-diselenide mixed system, successfully. Furthermore, we have developed new sequential addition of diselenide to acetylenes, olefins, and isocyanides. During these investigations, we have also found a novel four-component coupling reaction of diselenide with acetylene and two types of olefins via selective radical cyclization. As indicaled above, heteroatom-mixed systems attain selective introduction of a wide variety of heterofunctional groups into organic molecules.

我们开发了一系列杂原子-混合自由基反应体系，涉及第15、16和17族杂原子化合物。详细考察了杂原子自由基对碳-碳不饱和化合物和碳-氮不饱和化合物的反应活性。结果发现，硫代自由基对这些不饱和化合物具有很好的反应活性，二硒化物也表现出很好的捕获碳自由基的能力。因此，在光照条件下，二硫化物和二硒化物的混合体系提供了一种有用的方法，可以将硫基和硒基团选择性地引入到各种不饱和化合物中，如乙炔、烯烃、烯、共轭双烯、乙烯基环丙烷和异腈。这一原理可成功地应用于二硫化物-二碲化物混合体系、二硒化物-二碲碳化物混合体系、全氟烷基碘-二硒化物混合体系。此外，我们还开发了新的二硒醚与乙炔、烯烃和异氰化物的顺序加成反应。在这些研究中，我们还发现了二硒醚与乙炔和两种类型的烯烃通过选择性自由基环化反应的一种新的四组分偶联反应。如上所述，杂原子混合体系实现了在有机分子中选择性地引入各种杂化官能团。