Group 11 Metal Amide-Catalyzed Asymmetric Cycloaddition Reactions of Azomethine Imines with Terminal Alkynes
Group 11 Metal Amide-Catalyzed Asymmetric Cycloaddition Reactions of Azomethine Imines with Terminal Alkynes
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DOI：
10.1021/ja311150n
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发表时间：
2012-12-12
影响因子：
15
通讯作者：
Kobayashi, Shu
中科院分区：
文献类型：
--
作者：
Imaizumi, Takaki;Yamashita, Yasuhiro;Kobayashi, Shu
我们发展了一种偶氮甲亚胺与末端炔的1，3-偶极环加成反应，得到了N，N-双环吡唑烷酮衍生物。该反应以独特的5，7-二取代方式得到环加合物。此外，我们成功地将这种催化剂应用于不对称反应，并以高收率产生所需的杂环化合物，具有独特的区域选择性和高的对映选择性。机理研究阐明了一个逐步的反应途径和关键功能，确定区域选择性。
We developed a 1,3-dipolar cycloaddition reaction of azomethine imines with terminal alkynes catalyzed by group 11 metal amides to provide N,N-bicyclic pyrazolidinone derivatives. This reaction afforded the cycloadducts in a unique 5,7-disubstituted manner. Furthermore, we succeeded in applying this catalysis to asymmetric reactions, and the desired heterocycles were produced in high yields with exclusive regioselectivity and high enantioselectivity. Mechanistic studies elucidated a stepwise reaction pathway and critical features that determine the regioselectivity.