Development of Heteroatom Mixed Radical Reaction Systems

我们发展了一系列杂原子混合自由基反应体系，涉及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。作为结果，我们发现硫代自由基对这些不饱和化合物具有优异的反应性，并且二硒醚显示出优异的碳自由基捕获能力。因此，二硫化物和二硒化物的混合体系在光照射条件下提供了一种有用的方法，用于以良好的产率区域选择性地将硫基和硒基引入各种不饱和化合物，如乙炔、烯烃、丙二烯、共轭二烯、乙烯基环丙烷和异腈。该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-二碲化物混合体系、全氟烷基碘-二硒化物混合体系。此外，我们开发了新的顺序加成二硒化物的乙炔，烯烃，和异腈。在这些研究中，我们还发现了一个新的四组分偶联反应，二硒醚与乙炔和两种烯烃通过选择性自由基环化反应。如上所述，杂原子混合体系实现了将各种各样的杂官能团选择性地引入到有机分子中。

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.