Development of Catalytic Behavior of Borderline Metal complexes and Its Applications for Organic Synthesis

研究了边界金属催化的氨基烯环异构化反应。在反应中，我们发现三氟化铋是比其他过渡金属催化剂更有效的催化剂。铋催化的氢胺化反应可用于氨基-烯烃和氨基-烯烃与活性烯烃和苯甲醇的串联氢胺化反应，以较高的产率得到多取代N-杂环。此外，我们还开发了阳离子铁催化的烯烃分子内氢芳基化反应。在该反应中，阳离子铁催化剂有效地促进了具有强吸电子基团的缺电子芳烃与炔烃的加成反应。与其他类似氢胺化反应的传统催化剂相比，这种反应活性是非常独特的。

Borderline metal-catalyzed cycloisomerization of amino-allenes were investigated. In the reaction, we found that bismuth(III) triflate were more effective catalyst to proceed the reaction than other transition metal catalysts. The bismuth-catalyzed hydroamination can be applied to tandem ene-hydroamination of amino-allenes and amino-olefins with activated olefins and benzyl alcohols to provide multi-substituted N-heterocycles in good yields. In addition, we developed a cationic iron-catalyzed intramolecular hydroarylation of alkynes. In this reaction, the cationic iron catalyst promoted the addition of electron deficient arenes possessing strong electron-withdrawing group to alkynes, efficiently. This reactivity was very unique in comparison with other traditional catalysts for the similar hydroamination.