直接不对称的化N-甲基和N-胺用Ir(III) H催化剂
Ernest Salomó1, Albert Gallen2, Giuseppe Sciortino3,4
1Institute for Research in Biomedicine (IRB Barcelona), Barcelona Institute of Science and Technology , Baldiri Reixac 10 , 08028 Barcelona , Spain.
Journal of the American Chemical Society
|November 27, 2018
概括
这项研究引入了一种新型的催化剂,用于不对称的伊米因化,首次实现高反选择性. 催化剂
科学领域:
- 有机金属化学
- 不对称的催化
- 合成有机化学
背景情况:
- 直接不对称的化是有机合成中的关键转化.
- 开发高效和选择性的催化系统仍然是一个重大挑战.
- 复合物因其独特的反应性而越来越多地被用于化反应.
研究的目的:
- 开发一种用于直接非对称化N-甲基和N-胺的新型阴阳催化剂.
- 在这种转化中实现高的反选择性,此前没有报告.
- 研究催化剂结构和反应条件对催化性能的影响.
主要方法:
- 一种具有P-类固醇MaxPHOX连接体的新型阴阳性复合物的合成.
- 在各种N-甲基和N-胺的直接不对称化中应用催化剂.
- 使用密度功能理论 (DFT) 计算来合理化反应机制和立体化学结果.
主要成果:
- 开发的催化系统实现了高反选择性 (高达94% ee) 对于不对称的胺化.
- 这代表了第一个报告这种基质类别的高反选择性催化系统.
- 即使在低温下,可变四水 (THF) 连接物也促进了有效的催化剂激活和高反应性.
结论:
- 已成功开发出一种新且高度对酶选择性的催化剂系统.
- 在实现高立体控制方面,P-类固醇的MaxPHOX配体起着至关重要的作用.
- DFT计算为反应的立体化学过程提供了宝贵的见解,有助于未来的催化剂设计.
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