Catalyst-Controlled Aliphatic C–H Oxidations with a Predictive Model for Site-Selectivity

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.

选择性脂肪族碳氢键氧化反应对合成化学具有深远影响，因为碳氢键广泛存在于各类有机分子之中。实现该目标的核心，是具备宽泛底物适配范围（类小分子催化剂）的催化剂，它们可精准调控并强化或颠覆底物本身固有的氧化反应活性偏好（类酶催化剂）。本研究报道了一款简易的小分子非血红素铁催化剂，可在多种拓扑结构各异的底物上，以制备级收率实现可预测的催化剂主导型位点选择性氧化。所建立的催化剂反应活性模型，可将底物的固有物理性质与因催化剂不同而呈现的位点选择性进行定量关联。