| 第一作者： | Qi, FF (Qi, Feifei); Zhang, W (Zhang, Wei); Xue, YY (Xue, Yingying); Geng, C (Geng, Ce); Huang, XN (Huang, Xuenian); Sun, J (Sun, Jia); Lu, XF (Lu, Xuefeng); |
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| 联系作者： | Qi, FF (Qi, Feifei); Zhang, W (Zhang, Wei); Xue, YY (Xue, Yingying); Geng, C (Geng, Ce); Huang, XN (Huang, Xuenian); Sun, J (Sun, Jia); Lu, XF (Lu, Xuefeng); |
| 发表年度： | 2021 |
| 期： | 40 |
| 卷： | 143 |
| 页： | 16326-16331 |
| 摘要： | 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 O-18 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. |
| 刊物名称： | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY |
| 影响因子： | 14.695 |
| 全文链接： | https://pubs.acs.org/doi/10.1021/jacs.1c07182 |
