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Carbon-fluorine bond cleavage mediated by metalloenzymes.
Chemical Society Reviews ( IF 40.4 ) Pub Date : 2020-06-08 , DOI: 10.1039/c9cs00740g Yifan Wang 1 , Aimin Liu
Chemical Society Reviews ( IF 40.4 ) Pub Date : 2020-06-08 , DOI: 10.1039/c9cs00740g Yifan Wang 1 , Aimin Liu
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Fluorochemicals are a widely distributed class of compounds and have been utilized across a wide range of industries for decades. Given the environmental toxicity and adverse health threats of some fluorochemicals, the development of new methods for their decomposition is significant to public health. However, the carbon–fluorine (C–F) bond is among the most chemically robust bonds; consequently, the degradation of fluorinated hydrocarbons is exceptionally difficult. Here, metalloenzymes that catalyze the cleavage of this chemically challenging bond are reviewed. These enzymes include histidine-ligated heme-dependent dehaloperoxidase and tyrosine hydroxylase, thiolate-ligated heme-dependent cytochrome P450, and four nonheme oxygenases, namely, tetrahydrobiopterin-dependent aromatic amino acid hydroxylase, 2-oxoglutarate-dependent hydroxylase, Rieske dioxygenase, and thiol dioxygenase. While much of the literature regarding the aforementioned enzymes highlights their ability to catalyze C–H bond activation and functionalization, in many cases, the C–F bond cleavage has been shown to occur on fluorinated substrates. A copper-dependent laccase-mediated system representing an unnatural radical defluorination approach is also described. Detailed discussions on the structure–function relationships and catalytic mechanisms provide insights into biocatalytic defluorination, which may inspire drug design considerations and environmental remediation of halogenated contaminants.
中文翻译：
金属酶介导的碳-氟键断裂。
氟化物是一类分布广泛的化合物，几十年来已在各个行业得到广泛应用。鉴于某些含氟化合物的环境毒性和对健康的不利威胁，开发其分解新方法对公众健康具有重要意义。然而，碳-氟 (C-F) 键是化学性质最坚固的键之一。因此，氟化烃的降解异常困难。在这里，我们对催化这种具有化学挑战性的键断裂的金属酶进行了综述。这些酶包括组氨酸连接的血红素依赖性脱卤过氧化物酶和酪氨酸羟化酶、硫醇盐连接的血红素依赖性细胞色素P450和四种非血红素加氧酶，即四氢生物蝶呤依赖性芳香氨基酸羟化酶、2-酮戊二酸依赖性羟化酶、Rieske双加氧酶和硫醇双加氧酶。虽然有关上述酶的许多文献都强调它们催化 C-H 键活化和功能化的能力，但在许多情况下，C-F 键裂解已被证明发生在氟化底物上。还描述了代表非自然自由基脱氟方法的铜依赖性漆酶介导的系统。对结构-功能关系和催化机制的详细讨论提供了对生物催化脱氟的见解，这可能会激发药物设计考虑和卤化污染物的环境修复。
更新日期：2020-07-21
中文翻译：
金属酶介导的碳-氟键断裂。
氟化物是一类分布广泛的化合物，几十年来已在各个行业得到广泛应用。鉴于某些含氟化合物的环境毒性和对健康的不利威胁，开发其分解新方法对公众健康具有重要意义。然而，碳-氟 (C-F) 键是化学性质最坚固的键之一。因此，氟化烃的降解异常困难。在这里，我们对催化这种具有化学挑战性的键断裂的金属酶进行了综述。这些酶包括组氨酸连接的血红素依赖性脱卤过氧化物酶和酪氨酸羟化酶、硫醇盐连接的血红素依赖性细胞色素P450和四种非血红素加氧酶，即四氢生物蝶呤依赖性芳香氨基酸羟化酶、2-酮戊二酸依赖性羟化酶、Rieske双加氧酶和硫醇双加氧酶。虽然有关上述酶的许多文献都强调它们催化 C-H 键活化和功能化的能力，但在许多情况下，C-F 键裂解已被证明发生在氟化底物上。还描述了代表非自然自由基脱氟方法的铜依赖性漆酶介导的系统。对结构-功能关系和催化机制的详细讨论提供了对生物催化脱氟的见解，这可能会激发药物设计考虑和卤化污染物的环境修复。
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