A predictably selective aliphatic C-H oxidation reaction for complex molecule synthesis
A predictably selective aliphatic C-H oxidation reaction for complex molecule synthesis
复制标题
DOI：
10.1126/science.1148597
复制
发表时间：
2007-11-02
期刊：
影响因子：
56.9
通讯作者：
White, M. Christina
中科院分区：
文献类型：
--
作者：
Chen, Mark S.;White, M. Christina
实现有机合成中未活化的sp（3）C-H键氧化的非凡潜力需要发现既具有高反应性又具有可预测的选择性的催化剂。我们报道了一种铁（Fe）基小分子催化剂，其使用过氧化氢（H2 O2）来氧化广泛的底物。可预测的选择性仅基于C-H键的电子和空间性质实现，而不需要定向基团。另外，羧酸酯导向基团可用于提供五元环内酯产物。我们证明，这三种模式的选择性，使复杂的天然产物及其衍生物的可预测的氧化在特定的C-H键，具有显著有用的收益率。这种类型的一般和可预测的反应性使得脂肪族C-H氧化能够作为简化复杂分子合成的方法。
Realizing the extraordinary potential of unactivated sp(3) C-H bond oxidation in organic synthesis requires the discovery of catalysts that are both highly reactive and predictably selective. We report an iron (Fe)-based small molecule catalyst that uses hydrogen peroxide (H2O2) to oxidize a broad range of substrates. Predictable selectivity is achieved solely on the basis of the electronic and steric properties of the C-H bonds, without the need for directing groups. Additionally, carboxylate directing groups may be used to furnish five-membered ring lactone products. We demonstrate that these three modes of selectivity enable the predictable oxidation of complex natural products and their derivatives at specific C-H bonds with preparatively useful yields. This type of general and predictable reactivity stands to enable aliphatic C-H oxidation as a method for streamlining complex molecule synthesis.