Paul Melanie, Hoffmann Alexander, Herres-Pawlis Sonja
Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
J Biol Inorg Chem. 2021 May;26(2-3):249-263. doi: 10.1007/s00775-021-01849-9. Epub 2021 Feb 17.
Inspired by the efficiency of natural enzymes in organic transformation reactions, the development of synthetic catalysts for oxygenation and oxidation reactions under mild conditions still remains challenging. Tyrosinases serve as archetype when it comes to hydroxylation reactions involving molecular oxygen. We herein present new copper(I) guanidine halide complexes, capable of the activation of molecular oxygen at room temperature. The formation of the reactive bis(µ-oxido) dicopper(III) species and the influence of the anion are investigated by UV/Vis spectroscopy, mass spectrometry, and density functional theory. We highlight the catalytic hydroxylation activity towards diverse polycyclic aromatic alcohols under mild reaction conditions. The selective formation of reactive quinones provides a promising tool to design phenazine derivatives for medical applications.
受天然酶在有机转化反应中高效性的启发,开发在温和条件下用于氧化和氧化反应的合成催化剂仍然具有挑战性。在涉及分子氧的羟基化反应中,酪氨酸酶是典型代表。我们在此展示了新型卤化胍铜(I)配合物,其能够在室温下活化分子氧。通过紫外/可见光谱、质谱和密度泛函理论研究了活性双(μ-氧)二铜(III)物种的形成以及阴离子的影响。我们强调了在温和反应条件下对多种多环芳醇的催化羟基化活性。活性醌的选择性形成提供了一种有前景的工具,可用于设计用于医学应用的吩嗪衍生物。