Reductase of Mutanobactin Synthetase Triggers Sequential C-C Macrocyclization, C-S Bond Formation, and C-C Bond Cleavage.
Reductase of Mutanobactin Synthetase Triggers Sequential C-C Macrocyclization, C-S Bond Formation, and C-C Bond Cleavage.
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DOI：
10.1021/acs.orglett.9b04501
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发表时间：
2020-01
期刊：
影响因子：
5.2
通讯作者：
Min Wang;Zhoujie Xie;Shoubin Tang;E. L. Chang;Yue Tang;Zhengyan Guo;Yinglu Cui;Bian Wu;T. Ye;Yihua Chen
中科院分区：
文献类型：
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作者：
Min Wang;Zhoujie Xie;Shoubin Tang;E. L. Chang;Yue Tang;Zhengyan Guo;Yinglu Cui;Bian Wu;T. Ye;Yihua Chen
Mutanobactins （MUBs）及其同源物含有一个大环和/或一个噻吩环，是来自变形链球菌的脂肽，是龋齿的主要病原体。在这里，我们发现MubD的c端还原酶结构域以醛的形式释放脂己肽中间体，这使得自发的C-C大环化成为可能。在巯基的存在下，大环化的MUB可以进一步自发形成C-S键和C-C键裂解，生成多种MUB同系物。
Mutanobactins (MUBs) and their congeners that contain a macrocycle and/or a thiazepane ring are lipopeptides from Streptococcus mutans, a major causative agent of dental caries. Here we show that the C-terminal reductase domain of MubD releases the lipohexapeptide intermediates in an aldehyde form, which enables a spontaneous C-C macrocyclization. In the presence of a thiol group, the macrocyclized MUBs can further undergo spontaneous C-S bond formation and C-C bond cleavage to generate diverse MUB congeners.