Enzymes that proceed through radical intermediates have a rich chemistry that includes functionalization of otherwise unreactive carbon atoms, carbon‐skeleton rearrangements, aromatic reductions, and unusual eliminations. Especially under anaerobic conditions, organisms have developed a wide range of approaches for managing these transformations that can be exploited to generate new biological routes towards both bulk and specialty chemicals. These routes are often either much more direct or allow access to molecules that are inaccessible through standard (bio)chemical approaches. This review gives an overview of some of the key enzymes in this area: benzoyl‐CoA reductases effecting the enzymatic Birch reduction, ketyl radical dehydratases, coenzyme B₁₂‐dependent enzymes, glycyl radical enzymes, and radical SAM (AdoMet radical) enzymes. These enzymes are discussed alongside biotechnological applications, highlighting the wide range of actual and potential uses. With the increased diversity in biotechnological approaches to obtaining these enzymes and information about them, even more of these enzymes can be expected to find application in industrial processes.

中文翻译：

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生物技术厌氧自由基酶

通过自由基中间体产生的酶具有丰富的化学性质，包括原本不会发生反应的碳原子的官能化，碳骨架的重排，芳族化合物的还原以及不寻常的消除。尤其是在厌氧条件下，生物体已开发出多种方法来管理这些转化，可利用这些方法来生成针对批量化学品和特种化学品的新生物路线。这些途径通常更为直接，或者可以访问通过标准（生物）化学方法无法接近的分子。这篇综述概述了该领域的一些关键酶：影响酶促桦木还原的苯甲酰辅酶A还原酶，酮基脱水酶，辅酶B ₁₂依赖型酶，糖基自由基酶和自由基SAM（AdoMet自由基）酶。这些酶与生物技术应用一起进行了讨论，强调了广泛的实际和潜在用途。随着获得这些酶和有关它们的信息的生物技术方法的多样性的增加，可以期望在工业过程中找到更多的这些酶。