光诱导铜催化不对称的C-O交叉合
Jun Chen1, Yu-Jie Liang2, Peng-Zi Wang1
1CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, People's Republic of China.
Journal of the American Chemical Society
|August 11, 2021
概括
这项研究引入了一种新型的铜催化反应,用于使用氧化和二烯形成碳氧键. 这种方法在室温下实现了高选择性,为有机合成提供了新的工具.
科学领域:
- 有机化学
- 催化剂
- 摄影化学
背景情况:
- 在有机化学中,碳-异原子键的形成至关重要.
- 在C-N结合形成的进展与C-O结合形成的进展有限.
- 激素参与的催化不对称合成是一个活跃的研究领域.
研究的目的:
- 开发一种催化不对称C-O键形成的方法.
- 使用随时可用的oxime和1,3-dienes.
- 在合成基中实现高的区域和酶选择性.
主要方法:
- 光诱导铜催化交叉合反应
- 使用氧胺作为双功能试剂.
- 使用单一的,地球上丰富的合铜催化剂.
- 在紫色发光二极管 (LED) 照射下进行室温反应.
- 密度函数理论 (DFT) 的计算研究.
主要成果:
- 合成超过75种多种替代的基.
- 获得高区域和抗选择性 (高达95% ee).
- 证明了催化剂在光反氧催化和不对称诱导中的双重作用.
- 通过基极交叉提出了涉及π-铜中间体的反应机制.
结论:
- 一种新且高效的光诱导铜催化方法用于不对称的C-O键形成.
- 这种反应提供了一种具有优异选择性的基的多功能途径.
- 这些发现进一步拓展了催化不对称合成和光电还原催化领域.
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