Csp3-Csp3 从定义良好的铜 (III) 复合物中形成约束的减少消除
Matthew Paeth1, Sam B Tyndall1, Liang-Yu Chen2
1Department of Chemistry and Biochemistry , Miami University , Oxford , Ohio 45056 , United States.
Journal of the American Chemical Society
|January 26, 2019
概括
研究人员合成了稳定的有机铜 (III) 复合物以形成碳-碳键. 这些复合物通过还原性消除有效地产生基CF3产物,推进铜催化反应.
科学领域:
- 有机金属化学
- 催化剂
- 合成化学
背景情况:
- 铜催化反应对于有机合成至关重要.
- 有机铜 (III) 复合物是关键的中间体,但很少被分离出来.
- 在这些物种中通过减少性消除形成Csp3-Csp3键是特别具有挑战性的.
研究的目的:
- 开发一种合成稳定器官铜III复合物的一般方法.
- 调查这些复合物的减少Csp3-CF3键形成.
- 阐明这种减少消除过程的机制.
主要方法:
- 合成 [-CuIII-(CF3) 3-复合物.
- 使用NMR光谱,质谱和X射线晶体学进行结构性表征.
- 动力学研究和密度功能理论 (DFT) 的计算.
主要成果:
- 一系列明确的[alkyl-CuIII-(CF3) 3-复合物已成功合成和表征.
- 这些复合物在高温下经历第一阶降解,产生高达91%的基CF3产物.
- 动力学和DFT研究显示,Csp3-CF3键形成的协调过渡状态具有20kcal/mol的障碍.
结论:
- 稳定的器官铜 (III) 复合物可以合成,并作为Csp3-CF3键形成的有效前体.
- 通过协调的机制进行了减量消除,为铜催化交叉合反应提供了有价值的见解.
- 这项工作为合成三甲基化合物提供了新的途径.
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