Development of Heteroatom Mixed Radical Reaction Systems

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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.