Bienzyme-Catalytic and Dioxygenation-Mediated Anthraquinone Ring Opening,Journal of the American Chemical Society

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Bienzyme-Catalytic and Dioxygenation-Mediated Anthraquinone Ring Opening
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-09-29 , DOI: 10.1021/jacs.1c07182
Feifei Qi _{1,

2,

3} , Wei Zhang _{1,

2,

3,

4} , Yingying Xue ₅ , Ce Geng _{1,

2,

3} , Xuenian Huang _{1,

2,

3,

4} , Jia Sun ₅ , Xuefeng Lu _{1,

2,

3,

4,

6}

Affiliation

The C-10–C-4a bond cleavage of anthraquinone is believed to be a crucial step in fungal seco-anthraquinone biosynthesis and has long been proposed as a classic Baeyer–Villiger oxidation. Nonetheless, genetic, enzymatic, and chemical information on ring opening remains elusive. Here, a revised questin ring-opening mechanism was elucidated by in vivo gene disruption, in vitro enzymatic analysis, and ¹⁸O chasing experiments. It has been confirmed that the reductase GedF is responsible for the reduction of the keto group at C-10 in questin to a hydroxyl group with the aid of NADPH. The C-10–C-4a bond of the resultant questin hydroquinone is subsequently cleaved by the atypical cofactor-free dioxygenase GedK, giving rise to desmethylsulochrin. This proposed bienzyme-catalytic and dioxygenation-mediated anthraquinone ring-opening reaction shows universality.

中文翻译：

双酶催化和双加氧介导的蒽醌开环

蒽醌的 C-10–C-4a 键断裂被认为是真菌环蒽醌生物合成的关键步骤，并且长期以来被认为是经典的 Baeyer-Villiger 氧化。尽管如此，有关开环的遗传、酶学和化学信息仍然难以捉摸。在这里，通过体内基因破坏、体外酶分析和¹⁸ O 追逐实验阐明了修订后的 questin 开环机制。已证实还原酶 GedF 负责在 NADPH 的帮助下将 questin 中 C-10 的酮基还原为羟基。生成的 questin 对苯二酚的 C-10–C-4a 键随后被非典型的无辅因子双加氧酶 GedK 裂解，产生去甲基磺酰氯。这种双酶催化和双氧化介导的蒽醌开环反应显示出普遍性。

更新日期：2021-10-13

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