Development of Generation Method of Unstable Chemical Species Using Characteristics of Heteroatom Compounds

我们利用杂原子化合物的特性，研究了不稳定化学物种的新生成方法，并将其应用于有机合成。在我们的研究过程中，我们发现在催化量的硒存在下，一氧化碳还原芳香族硝基化合物可以有效地生成硝基或类硝基物种。在硒的催化下，邻硝基苯乙烯、邻硝基苯甲酰胺与一氧化碳反应合成了吲哚和4(~3H)-喹唑烷酮等N-杂环化合物，产率中等到较高。此外，我们还开发了通过1，2，3-硒二唑热分解生成乙烯基自由基的新方法。当1，2，3-硒二唑在热条件下与烯烃反应时，原位生成的乙烯基加成到碳-碳双键上，然后进行分子内环合反应，得到相应的二氢硒并以较高的产率得到相应的二氢硒。添加催化量的有机锡自由基对该反应几乎没有促进作用。

We have investigated the new generation method of unstable chemical species by the use of the characteristics of heteroatom compounds and the utilization of these species in organic synthesis. In the course of our study, we found that nitre or nitrenoid species were generated efficiently by the reduction of aromatic nitro compounds with carbon monoxide in the presence of a catalytic amount of selenium. N-Heterocyclic compounds such as indols and 4(3H)-quinazolinones were synthesized by the selenium-catalyzed reaction of 0-nitrostyrenes and 0-nitrobenzoylamides with carbon monoxide in moderate to good yields. In addition, we have also developed the new generation method of vinyl radical via the thermal decomposition of 1,2,3-selenadiazoles. When 1,2,3-selenadiazoles were treated with olefins under thermal condition, the addition of vinyl radical generated in situ to carbon-carbon double bond and followed by intramoleculer cyclization proceeded efficiently to give the corresponding dihydroselenophenes in moderated to good yields. This reaction was hardly promoted by the addition of a catalytic amount of organostannyl radical.