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氧中性,铁介导的C-H激活:一般原则和机制见解

Tianyi Zhang¹, William G Whitehurst¹, Matthew V Pecoraro¹

¹Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.

Journal of the American Chemical Society

|October 25, 2024

概括

铁 (II) 复合物可实现氧化中性C-H激活,用于对pivalophenone进行定向甲基化. 反应速率取决于配体可变性,铁自旋状态和配体类型,为C-H功能化提供一种一般方法.

科学领域:

有机金属化学
催化剂
C-H 激活

背景情况:

在高效的有机合成中,C-H活性是至关重要的.
铁复合物为贵金属催化剂提供了可持续的替代品.
了解控制铁介导C-H功能化的原理是开发新催化方法的关键.

研究的目的:

建立使用铁 (II) 复合物的氧化还原中性C-H激活的一般原则.
调查皮瓦洛的区域选择性C(sp2) -H甲基化.
阐明影响铁介导C-H功能化的速度和选择性的因素.

主要方法:

使用铁二甲基复合物的实验研究,包括 (depe) 2Fe 2CH 3
分析反应途径和电子效应的计算研究.
动力学研究和乳标记以确定反应机制.

主要成果:

实现了针对性,区域选择性C ((sp2) -H甲基化.
反应速率受素连接体可变性,铁自旋状态和X型连接体大小的影响.
化反应显示了各种基质与指导组的普遍性.
和是最佳的基质,与多种固态环境和酸性α相容.
确定了轨道杂交对化学选择性的影响,其中具有较高s字符的Fe-R键促进了选择性C-H激活.

结论:

铁 (II) 复合物可以有效调解氧化-中性C-H激活和功能化.
铁中心的连接体设计和电子特性对于控制反应性和选择性至关重要.
这项研究提供了铁催化C-H激活的机理理解,为新的合成应用铺平了道路.

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