循环α-二碳化合物的Rh催化分子间反应具有对三级C-H键迁移的选择性
Andrew DeAngelis1, Olga Dmitrenko, Joseph M Fox
1Brown Laboratories, Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
Journal of the American Chemical Society
|June 9, 2012
概括
新的Rh催化反应使用循环二碳烯化合物实现了选择性的分子间转化. 这些方法克服了固体障碍,促进了循环和X-H插入各种基质.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
背景情况:
- 化学选择性反应在有机合成中至关重要.
- Rh-碳化合物是多用途的中间体,但通常面临的挑战是选择性比竞争的途径,如β-化物消除.
研究的目的:
- 开发循环α-碳化合物的新型分子间Rh催化反应.
- 为了实现对β-化物消除的化学选择性.
- 探索这些新变化的范围和局限性.
主要方法:
- 使用循环α-二碳烯化合物作为Rh-carbenoids的前体.
- 研究的分子间反应包括环,环和X-H插入.
- 用人密度函数理论 (DFT) 计算以支持机械学建议.
主要成果:
- 证明了第一个在三级β-C-H键迁移上具有选择性的一般分子间Rh-carbenoid反应.
- 通过广泛的基板实现了成功的转换.
- 确定了影响反应性的固态和形状因素,特别是对于七个环的环.
结论:
- 循环α-碳酸化合物,特别是五和六个环,通过增强碳联来促进分子间Rh催化反应.
- 较大的环的硬性和形状灵活性会阻碍分子间反应.
- 开发的方法为选择性有机合成提供了一个强大的新工具.
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