Ottenbacher Roman V, Talsi Evgenii P, Bryliakov Konstantin P
Chemistry Department, Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russia.
Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russia.
Molecules. 2016 Oct 31;21(11):1454. doi: 10.3390/molecules21111454.
Non-heme iron(II) complexes are widespread synthetic enzyme models, capable of conducting selective C-H oxidation with H₂O₂ in the presence of carboxylic acid additives. In the last years, structurally similar manganese(II) complexes have been shown to catalyze C-H oxidation with similarly high selectivity, and with much higher efficiency. In this mini-review, recent catalytic and mechanistic data on the selective C-H oxygenations with H₂O₂ in the presence of manganese complexes are overviewed. A distinctive feature of catalyst systems of the type Mn complex/H₂O₂/carboxylic is the existence of two alternative reaction pathways (as found for the oxidation of cumenes), one leading to the formation of alcohol, and the other to ester. The mechanisms of formation of the alcohol and the ester are briefly discussed.
非血红素铁（II）配合物是广泛存在的合成酶模型，能够在羧酸添加剂存在下用H₂O₂进行选择性C-H氧化。在过去几年中，结构相似的锰（II）配合物已被证明能以同样高的选择性和更高的效率催化C-H氧化。在这篇综述中，概述了在锰配合物存在下用H₂O₂进行选择性C-H氧化的最新催化和机理数据。Mn配合物/H₂O₂/羧酸这类催化剂体系的一个显著特点是存在两条替代反应途径（如在异丙苯氧化中发现的），一条导致醇的形成，另一条导致酯的形成。简要讨论了醇和酯的形成机制。
