首页> 外文期刊>Journal of the American Chemical Society >Substrate and Lewis Acid Coordination Promote 0-0 Bond Cleavage of an Unreactive L_2Cu~(||)_2(O_2~(2-)) Species to Form L_2Cu~|||_2(O)_2 Cores with Enhanced Oxidative Reactivity
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Substrate and Lewis Acid Coordination Promote 0-0 Bond Cleavage of an Unreactive L_2Cu~(||)_2(O_2~(2-)) Species to Form L_2Cu~|||_2(O)_2 Cores with Enhanced Oxidative Reactivity

机译:底物和路易斯酸配位促进未反应的L_2Cu〜(||)_2(O_2〜(2-))物种的0-0键裂解,形成具有增强的氧化反应性的L_2Cu〜||| _2(O)_2核

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摘要

Copper-dependent metalloenzymes are widespread throughout metabolic pathways, coupling the reduction of O_2 with the oxidation of organic substrates. Small-molecule synthetic analogs are useful platforms to generate L/Cu/O_2 species that reproduce the structural, spectroscopic, and reactive properties of some copper-/O_2-dependent enzymes. Landmark studies have shown that the conversion between dicopper(Ⅱ)-peroxo species (L_2Cu~(||)_2O_2~(2-)) either side-on peroxo, ~SP, or end-on trans-peroxo, ~TP) and dicopper(III)-bis(μ-oxo) (L_2Cu~(|||)_2(O~(2-))_2: O) can be controlled through ligand design, reaction conditions (temperature, solvent, and counteranion), or substrate coordination. We recendy published (J. Am. Chem. Soc. 2012, 134, 8513, DOI: 10.1021/ja300674m) the crystal structure of an unusual ~SP species [(MeAN)_2Cu~(II)_2(O_2~(2-))]~(2+) (~sP~(MeAN), MeAN: N-methyl-N,N-bis [3-(dimethylamino)propyl] amine) that featured an elongated O-O bond but did not lead to O-O cleavage or reactivity toward external substrates. Herein, we report that ~sp~(MeAN) can be activated to generate o~(MeAN) and perform the oxidation of external substrates by two complementary strategies: (i) coordination of substituted sodium phenolates to form the substrate-bound O~(MeAN)-RPhO species that leads to ortho-hydroxylation in a tyrosinase-like fashion and (ii) addition of stoichiometric amounts (l or 2 equiv) of Lewis acids (LA's) to form an unprecedented series of O-type species (0~(MeAN)-LA) able to oxidize C-H and O-H bonds. Spectroscopic, computational, and mechanistic studies emphasize the unique plasticity of the ~Sp~(MeAN) core, which combines the assembly of exogenous reagents in the primary (phenolates) and secondary (Lewis acids association to the MeAN ligand) coordination spheres with O-O cleavage. These findings are reminiscent of the strategy followed by several metalloproteins and highlight the possible implication of O-type species in copper-/dioxygen-dependent enzymes such as tyrosinase (Ty) and particulate methane monooxygenase (pMMO).
机译:铜依赖性金属酶遍布代谢途径,将O_2的还原与有机底物的氧化结合在一起。小分子合成类似物是产生L / Cu / O_2物种的有用平台,这些物种可再现某些依赖铜/ O_2的酶的结构,光谱和反应特性。具有里程碑意义的研究表明,双铜(Ⅱ)-过氧物质(L_2Cu〜(||)_2O_2〜(2-))在侧向过氧(〜SP)或端侧反式过氧(〜TP)和双铜(III)-双(μ-氧代)(L_2Cu〜(|||)_2(O〜(2-))_ 2:O)可通过配体设计,反应条件(温度,溶剂和抗衡阴离子)控制,或基材配合。我们建议发表(J. Am。Chem。Soc。2012,134,8513,DOI:10.1021 / ja300674m)一种不常见的〜SP物种[(MeAN)_2Cu〜(II)_2(O_2〜(2-) )]〜(2+)(〜sP〜(MeAN),MeAN:N-甲基-N,N-双[3-(二甲基氨基)丙基]胺)具有延长的OO键,但没有导致OO裂解或对外部底物的反应性。在本文中,我们报道〜sp〜(MeAN)可以被激活以生成o〜(MeAN)并通过两种互补策略进行外部底物的氧化:(i)取代酚钠的配位形成与底物结合的O〜( (MeAN)-RPhO物种以类似酪氨酸酶的方式导致邻羟基化,并且(ii)添加化学计量量(1或2当量)的路易斯酸(LA),形成前所未有的一系列O型物种(0〜 (MeAN)-LA)能够氧化CH和OH键。光谱,计算和机理研究强调〜Sp〜(MeAN)核的独特可塑性,该结合将外源试剂在一级(酚盐)和二级(路易斯酸与MeAN配体的缔合)配位领域中的组装与OO裂解相结合。这些发现让人想起了随后的几种金属蛋白的策略,并突显了O型物质可能与铜/双氧依赖性酶(例如酪氨酸酶(Ty)和颗粒甲烷单加氧酶(pMMO))有关。

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  • 来源
    《Journal of the American Chemical Society》 |2017年第8期|3186-3195|共10页
  • 作者单位

    Department of Chemistry, Southern Methodist University, Dallas, Texas 75275, United States;

    Department of Chemistry, Stanford University, Stanford, California 94305, United States;

    Johns Hopkins University, Baltimore, Maryland 21218, United States;

    Johns Hopkins University, Baltimore, Maryland 21218, United States;

    Department of Chemistry, Stanford University, Stanford, California 94305, United States;

    Johns Hopkins University, Baltimore, Maryland 21218, United States;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
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  • 入库时间 2022-08-18 03:07:55

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