通过动态基质/接质/稀土金属集聚物的不对称催化
Akihiro Nojiri1, Naoya Kumagai, Masakatsu Shibasaki
1Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-0033 Tokyo, Japan.
Journal of the American Chemical Society
|April 9, 2008
概括
这项研究详细介绍了一种高度选择性的催化不对称的Mannich型反应,使用alpha-cyanoketones和N-Boc imines. 这些发现表明,即使没有预先复杂化,组件也会形成有序的过渡状态.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 不对称的合成方法
背景情况:
- 曼尼希反应是一种基本的碳-碳键形成反应.
- 在曼尼赫类反应中实现高的enantio和 diastereoselectivity仍然是一个挑战.
- 催化不对称合成提供了有效的途径,以奇拉分子.
研究的目的:
- 开发一种高度分离和分离选择的催化不对称的曼尼赫型反应.
- 调查催化剂预复杂化在反应机制中的作用.
- 为了阐明反应过程中过渡状态的形成.
主要方法:
- 使用了一种胺基连接物/ (III) 三叶酸催化剂系统.
- 作为基质使用了α-基和N-Boc imines.
- 分析了具有和没有催化剂预复杂化的反应结果.
- 收集了光谱数据并进行了艾灵分析.
主要成果:
- 在曼尼赫型反应中实现了高的enantio和 diastereoselectivity.
- 观察到类似的反应结果,无论催化剂预复杂化.
- 光谱数据和艾灵图表支持从一个无序的混合物中形成一个有序的过渡状态.
- 证明了胺基联体/Sc(OiPr) 3系统的催化效率.
结论:
- 催化不对称的曼尼赫式反应提供了一种选择性合成性化合物的方法.
- 反应通过在现场形成的有序过渡状态进行.
- 催化剂预复杂化对于在这个系统中实现高选择性是不必要的.
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