从氧/二烯 (3+2) 循环添加物中选择性形成5 - 乙二甲的起源 Pd(0) 催化
Yike Zou1, Shuming Chen1, K N Houk1
1Department of Chemistry and Biochemistry , University of California , Los Angeles , California 90095-1569 , United States.
Journal of the American Chemical Society
|July 23, 2019
概括
这项研究揭示了缺乏电子的氧 (Pd-oxyallyl) 循环添加与结合的二烯通过一个阶段性机制进行. 计算分析突出了替代剂在促进C-C键形成中的作用.
科学领域:
- 有机金属化学
- 有机合成
- 计算化学
背景情况:
- 催化循环添加在有机合成中至关重要.
- 了解反应机制是优化合成路径的关键.
研究的目的:
- 研究缺乏电子的Pd-oxyallyls和结合的dienes之间的 (3+2) 循环添加的机制.
- 阐明影响反应性和选择性的因素.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 对反应路径,过渡状态和电子性质的分析.
主要成果:
- 具有初始C-C键形成的阶段性机制得到了计算支持.
- 提取电子的替代剂降低了LUMO能量,减少了迁移插入障碍.
- 由于更高的插入障碍和C-O消除障碍,单烯反应不受欢迎.
- 结合的二烯有助于电友 η3 Pd-基物种的形成和 C-O 键的形成.
结论:
- 该研究提供了关于Pd-oxyallyl循环添加物的详细机制见解.
- 替代剂和二烯结合对于有效的循环添加反应至关重要.
- DFT计算对于预测和理解有机金属催化反应有价值.
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