Formation and Cleavage of C-C Bonds by Enzymatic Oxidation-Reduction Reactions.

Formation and Cleavage of C-C Bonds by Enzymatic Oxidation-Reduction Reactions.
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DOI:
10.1021/acs.chemrev.8b00031
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发表时间:
2018-07-25
期刊:
影响因子:
62.1
通讯作者:
Yoshimoto FK
Yoshimoto FK
中科院分区:
化学1区
文献类型:
--
作者:
Guengerich FP;Yoshimoto FK

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许多氧化还原酶,特别是加氧酶,在形成和破坏C-C键的反应中起作用。该列表包括细胞色素P450和其他基于血红素的单加氧酶、基于血红素的双加氧酶、非血红素铁单加氧酶和双加氧酶、黄素蛋白、自由基S-腺苷甲硫氨酸酶、铜酶和过氧化物酶。反应涉及类固醇,中间代谢,次级天然产物,药物和工业和农业化学品。许多C-C键通过(i)双自由基的偶联或(ii)产生重排的不稳定产物而形成。C-C裂解反应涉及几个主题:(i)由酶产生的不稳定氧化产物的重排,(ii)通过重排的自由基或阳离子的氧化和崩溃,(iii)氧化以产生易于被其他酶水解的产物,以及(iv)在底物结合促进O2活化的系统中O2的活化。许多酶都涉及金属,但其中铁显然占主导地位。
Many oxidation-reduction (redox) enzymes, particularly oxygenases, have roles in reactions that make and break C-C bonds. The list includes cytochrome P450 and other heme-based monooxygenases, heme-based dioxygenases, non-heme iron mono- and dioxygenases, flavoproteins, radical S-adenosylmethionine enzymes, copper enzymes, and peroxidases. Reactions involve steroids, intermediary metabolism, secondary natural products, drugs, and industrial and agricultural chemicals. Many C-C bonds are formed via either (i) coupling of diradicals or (ii) generation of unstable products that rearrange. C-C cleavage reactions involve several themes: (i) Rearrangement of unstable oxidized products produced by the enzymes, (ii) oxidation and collapse of radicals or cations via rearrangement, (iii) oxygenation to yield products that are readily hydrolyzed by other enzymes, and (iv) activation of O2 in systems in which the binding of a substrate facilitates O2 activation. Many of the enzymes involve metals, but of these iron is clearly predominant.
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