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

研究了边缘金属催化的氨基烯环异构化反应。在反应中，我们发现三酸铋（III）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以应用于氨基烯烯和氨基烯烃与活性烯烃和苯甲醇的串联烯-氢胺化反应，得到收率高的多取代n -杂环。此外，我们还开发了一种阳离子铁催化的炔分子内氢化芳基化反应。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在炔上的加成。与其他传统催化剂相比，这种反应性是非常独特的。

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.