Tricarbocyclic core formation of tyrosine-decahydrofluorenes implies a three-enzyme cascade with XenF-mediated sigmatropic rearrangement as a prerequisite

查看全文 作　　者：Zhiguo [1]Liu;Wei [2,3]Li;Peng [2]Zhang;Jie [2]Fan;Fangbo [1]Zhang;Caixia [1]Wang;Shuming [4]Li;Yi [1]Sun;Shilin [1]Chen;Wenbing [2,3]Yin

机构地区：[1]Institute of Chinese Materia Medica,China Academy of Chinese Medical Sciences,Beijing 100700,China;[2]State Key Laboratory of Mycology,CAS Key Laboratory of Microbial Physiological and Metabolic Engineering,Institute of Microbiology,Chinese Academy of Sciences,Beijing 100101,China;[3]Savaid Medical School,University of Chinese Academy of Sciences,Beijing 100049,China;[4]Institut für Pharmazeutische Biologie und Biotechnologie,Fachbereich Pharmazie,Philipps-Universitat Marburg,Marburg 35037,Germany

出　　处：《Acta Pharmaceutica Sinica B》索引2021年第11卷第11期,共10页

基　　金：supported in part by National Key Research and Development Program of China(2020YFA0907800 and 2018YFC1706104);National Natural Science Foundation of China(31861133004 and 81502968);the Deutsche Forschungsgemeinschaft(DFG,German Research Foundation Li844/11-1,Germany);Key Research Program of Frontier Sciences,CAS(ZDBS-LY-SM016,China)。 摘　　要：Tyrosine-decahydrofluorene derivatives feature a fused[6.5.6]tricarbocyclic core and a 13-membered para-cyclophane ether.Herein,we identified new xenoacremones A,B,and C(1-3)from the fungal strain Xenoacremonium sinensis ML-31 and elucidated their biosynthetic pathway using gene deletion in the native strain and heterologous expression in Aspergillus nidulans.The hybrid polyketide synthaseenonribosomal peptide synthetase(PKS-NRPS)XenE together with enoyl reductase XenG were confirmed to be responsible for the formation of the tyrosine-nonaketide skeleton.This skeleton was subsequently dehydrated by XenA to afford a pyrrolidinone moiety.XenF catalyzed a novel sigmatropic rearrangement to yield a key cyclohexane intermediate as a prerequisite for the formation of the multi-ring system.Subsequent oxidation catalyzed by XenD supplied the substrate for XenC to link the para-cyclophane ether,which underwent subsequent spontaneous Diels-Alder reaction to give the end products.Thus,the results indicated that three novel enzymes XenF,XenD,and XenC coordinate to assemble the[6.5.6]tricarbocyclic ring and para-cyclophane ether during biosynthesis of complex tyrosine-decahydrofluorene derivatives. 关键词：Tyrosine-decahydrofluorene BIOSYNTHESIS PKS-NRPS Xenoacremone Heterologous expression

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Tricarbocyclic core formation of tyrosine-decahydrofluorenes implies a three-enzyme cascade with XenF-mediated sigmatropic rearrangement as a prerequisite

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