可见光激活的非对称β-C-H功能化受体替代与1,2-二二碳化合物
Jiajia Ma1, Anthony R Rosales2, Xiaoqiang Huang1
1Fachbereich Chemie, Philipps-Universität Marburg , Hans-Meerwein-Strasse 4, 35043 Marburg, Germany.
Journal of the American Chemical Society
|November 22, 2017
概括
这项研究引入了一种使用可见光和催化剂进行非对称C-H功能化的新方法. 反应有效地产生具有高立体选择性的复杂分子,促进有机合成.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 摄影化学的使用.
背景情况:
- 不对称的合成对于药品和材料至关重要.
- 为C-H功能化开发高效的催化系统仍然是一个挑战.
- 可见光光还原催化提供了一种可持续的方法来进行有机转化.
研究的目的:
- 开发一种新的可见光激活不对称β-C(sp3)-H功能化方法.
- 使用立体在的易斯酸催化剂来实现高立体控制.
- 通过实验和计算研究来探索反应机制.
主要方法:
- 用可见光对2 - 乙伊米达/皮里丁与1,2-二碳化合物进行辐射.
- 使用定制的立体在的易斯酸进行催化.
- 产品的隔离和净化.
- 立体选择性分析 (dr和ee的确定).
- 通过实验和计算方法进行机械研究.
主要成果:
- 高收益率 (高达99%) 的C-C债券形成产品.
- 优秀的立体选择性 (高达>20:1 dr和>99% ee).
- 确定一种反应机制,涉及光激活的Rh-酸盐,单电子转移,质子转移和根基-根基重组.
结论:
- 开发的方法为β-C(sp3)-H功能化提供了一个高效和高度刻板选择的途径.
- 催化剂的设计和可见光激活是实现高选活性的关键.
- 机械学的见解为设计用于不对称合成的新催化系统铺平了道路.
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