Characterizing Post-PKS Modifications of 16-Demethyl-rifamycin Revealed Two Dehydrogenases Diverting the Aromatization Mode of Naphthalenic Ring in Ansamycin Biosynthesis  

作　　者：Ting-Yan Han Kai Zhang Gong-Li Tang Qiang Zhou 

机构地区：[1]State Key Laboratory of Bio-organic and Natural Products Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,345 Lingling Road,Shanghai 200032,China [2]School of Chemistry and Materials Science,Hangzhou Institute for Advanced Study,University of Chinese Academy of Sciences,1Sublane Xiangshan,Hangzhou,Zhejiang 310024,China

出　　处：《Chinese Journal of Chemistry》2022年第13期1553-1558,共6页中国化学（英文版）

基　　金：We thank the financial support from the National Natural Science Foundation of China(22137009 and 21907067).

摘　　要：The anti-tuberculous rifamycins belong to naphthalenic ansamycin based on the structure of aromatic chromophore.Herein,we explored the post-polyketide synthase(PkS)modifications in the biosynthesis of 16-demethyl-rifamycins via gene knockout,complementation and in vitro enzyme assays.The collective evidences showed that i)the aromatization of 8-hydroxyl-7,8-dihydronaphtoquinone was accomplished by the combined action of two dehydrogenases,Rifs and Rif;i)the acetylation and methylation of the macrocycle was carried out on naphthoquinone intermediates in preference to naphthol,by Rif-Orf20 and Rif-Orf14,respectively ii)the presence of Rifs/T homologs in ansamycin biosynthetic gene clusters corresponds to the dehydrogenation aromatization mode of dihydronaphthalene.These findings cast new insights into the naphthalene formation and post-PkS modification of ansamycins.

关 键 词：Ansamycin Natural products BIOSYNTHESIS DEHYDROGENATION AROMATIZATION 

分 类 号：O62[理学—有机化学]