Southern Laboratories-208A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India.
Dalton Trans. 2023 Jun 27;52(25):8645-8653. doi: 10.1039/d3dt00697b.
Inspired by copper-based metalloenzymes, we aim to incorporate amino acids into our ligands to facilitate active copper intermediates that serve as functional and structural models for these enzymes. Herein, we report the synthesis of a Cu(II) complex with a symmetric proline-based pseudopeptide LH (,'-(ethane-1,2-diyl)bis(pyrrolidine-2-carboxamide)), which is capable of supporting an [(L)Cu(III)] (3) intermediate in MeOH : CHCN (1 : 20) at -30 °C. From comparative studies with the pyridine analog Cu(II) complex, it was demonstrated that the incorporation of amino acid in the ligand framework decreased the Cu(III)/Cu(II) redox potential significantly to react readily with CPBA and CAN. The newly generated [(L)Cu(III)] can promote hydrogen atom abstraction reactions with phenolic substrates.
受铜基金属酶的启发，我们旨在将氨基酸纳入配体中，以促进作为这些酶的功能和结构模型的活性铜中间体。在此，我们报告了一种具有对称脯氨酸基拟肽 LH (,'-(乙烷-1,2-二基)双(吡咯烷-2-甲酰胺))的 Cu(II)配合物的合成，该配合物能够在 MeOH:CHCN (1:20)在-30°C 下支持[(L)Cu(III)] (3)中间体。通过与吡啶类似物 Cu(II)配合物的比较研究表明，配体框架中氨基酸的掺入显著降低了 Cu(III)/Cu(II)氧化还原电位，使其能够与 CPBA 和 CAN 快速反应。新生成的[(L)Cu(III)]可以促进与酚类底物的氢原子提取反应。
