Artificial Metalloenzymes based on TetR Proteins and Cu(II) for Enantioselective Friedel-Crafts Alkylation Reactions.,ChemCatChem

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Artificial Metalloenzymes based on TetR Proteins and Cu(II) for Enantioselective Friedel-Crafts Alkylation Reactions.
ChemCatChem ( IF 3.8 ) Pub Date : 2020-04-17 , DOI: 10.1002/cctc.202000245
Cora Gutiérrez de Souza ₁ , Manuela Bersellini ₁ , Gerard Roelfes ₁

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The supramolecular approach is among the most convenient methodologies for creating artificial metalloenzymes (ArMs). Usually this approach involves the binding of a transition metal ion complex to a biomolecular scaffold via its ligand, which also modulates the catalytic properties of the metal ion. Herein, we report ArMs based on the proteins CgmR, RamR and QacR from the TetR family of multidrug resistance regulators (MDRs) and Cu²⁺ ions, assembled without the need of a ligand. These ArMs catalyze the enantioselective vinylogous Friedel‐Crafts alkylation reaction with up to 75 % ee. Competition experiments with ethidium and rhodamine 6G confirm that the reactions occur in the chiral environment of the hydrophobic pocket. It is proposed that the Cu²⁺‐substrate complex is bound via a combination of electrostatic and π‐stacking interactions provided by the second coordination sphere. This approach constitutes a fast and straightforward way to assemble metalloenzymes and may facilitate future optimization of the protein scaffolds via mutagenesis or directed evolution approaches.

中文翻译：

基于 TetR 蛋白和 Cu(II) 的人工金属酶，用于对映选择性 Friedel-Crafts 烷基化反应。

超分子方法是制造人工金属酶（ArM）最方便的方法之一。通常这种方法涉及过渡金属离子络合物通过其配体与生物分子支架结合，这也调节金属离子的催化特性。在此，我们报告了基于来自多药耐药调节因子 (MDR) TetR 家族的蛋白质 CgmR、RamR 和 QacR 和 Cu ²⁺离子的 ArM，无需配体即可组装。这些 ArM 催化对映选择性插烯 Friedel-Crafts 烷基化反应，ee 高达 75%。乙锭和罗丹明 6G 的竞争实验证实反应发生在疏水口袋的手性环境中。据推测，Cu ²⁺基底复合物是通过第二配位层提供的静电和 π 堆积相互作用的组合来结合的。这种方法构成了一种快速而直接的组装金属酶的方法，并且可能有助于未来通过诱变或定向进化方法优化蛋白质支架。

更新日期：2020-06-18

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