Catalyst-Controlled Aliphatic C-H Oxidations with a Predictive Model for Site-Selectivity
Catalyst-Controlled Aliphatic C-H Oxidations with a Predictive Model for Site-Selectivity
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DOI：
10.1021/ja407388y
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发表时间：
2013-09-25
影响因子：
15
通讯作者：
White, M. Christina
中科院分区：
文献类型：
--
作者：
Gormisky, Paul E.;White, M. Christina
选择性的脂肪族C-H键氧化可能对合成有深远的影响，因为这些键存在于所有类别的有机分子中。这一目标的核心是具有广泛底物范围(小分子样)的催化剂，可预测地增强或颠覆底物对氧化的固有反应性偏好(酶样)。我们报道了一种简单的小分子、非血红素铁催化剂，它在一系列拓扑结构不同的底物上实现了可预测的催化剂控制的位置选择性制备产率。催化剂反应性模型定量地将底物的固有物理性质与作为催化剂的函数观察到的位置选择性相关联。
Selective aliphatic C-H bond oxidations may have a profound impact on synthesis because these bonds exist across all classes of organic molecules. Central to this goal are catalysts with broad substrate scope (small-molecule-like) that predictably enhance or overturn the substrate's inherent reactivity preference for oxidation (enzyme-like). We report a simple small-molecule, non-heme iron catalyst that achieves predictable catalyst-controlled site-selectivity in preparative yields over a range of topologically diverse substrates. A catalyst reactivity model quantitatively correlates the innate physical properties of the substrate to the site-selectivities observed as a function of the catalyst.