Electrochemistry contributes a strong tool for the manufacture of molecules,addressing intractable challenges in synthetic chemistry by enabling innovative reaction pathways.Herein,a bifunctional reagent,aqueous hydro...Electrochemistry contributes a strong tool for the manufacture of molecules,addressing intractable challenges in synthetic chemistry by enabling innovative reaction pathways.Herein,a bifunctional reagent,aqueous hydrochloric acid,is used to establish an electrochemical selective dual-oxidation approach that gives access toα-chlorosulfoxides from sulfides.This strategy presents broad substrate scope,high diastereoselectivity,and regioselectivity.The late-stage modification of amino acids and pharmaceutical derivatives further highlights the utility.Furthermore,detailed mechanistic studies reveal that the key success for this selective chemical transformation is the dual-oxidation process at the anode.This electrochemical dual-oxidation strategy may have wide universality;we anticipate diverse applications of this protocol across the many fields of chemistry.展开更多
Genomic clustering of non-homologous genes for the biosynthesis of plant defensive compounds is an emerging theme, but insights into their formation and physiological function remain limited. Here we report the identi...Genomic clustering of non-homologous genes for the biosynthesis of plant defensive compounds is an emerging theme, but insights into their formation and physiological function remain limited. Here we report the identification of a newly discovered hydroxycinnamoyl tyramine(HT) gene cluster in rice.This cluster contains a pyridoxamine 50-phosphate oxidase(Os PDX3) producing the cofactor pyridoxal50-phosphate(PLP), a PLP-dependent tyrosine decarboxylase(Os Ty DC1), and two duplicated hydroxycinnamoyl transferases(Os THT1 and Os THT2). These members were combined to represent an enzymological innovation gene cluster. Natural variation analysis showed that the abundance of the toxic tyramine intermediate of the gene cluster among different rice accessions is mainly determined by the coordinated transcription of Os Ty DC1 and Os THT1. Further pathogen incubation assays demonstrated that the end products of the HT gene cluster displayed enhanced resistance to the bacterial pathogen Xanthomonas oryzae pv. Oryzae(Xoo) and fungal pathogen Magnaporthe oryzae(M. oryzae), and the enhanced resistance is associated with the boost of phytoalexins and the activation of defense response. The unique presence of the HT gene cluster in Oryza AA genome, together with the enrichment of transposon elements within this gene cluster region, provides an evolutionary background to accelerate cluster member combinations. Our study not only discovered a gene cluster involved in the phenylpropanoid metabolism but also addressed the key aspects of gene cluster formation. In addition, our results provide a new metabolic pool for plant defense against pathogens.展开更多
基金supported by the National Natural Science Foundation of China(22031008)Science Foundation of Wuhan(2020010601012192)The Program of Introducing Talents of Discipline to Universities of China(111 Program)is also appreciated。
文摘Electrochemistry contributes a strong tool for the manufacture of molecules,addressing intractable challenges in synthetic chemistry by enabling innovative reaction pathways.Herein,a bifunctional reagent,aqueous hydrochloric acid,is used to establish an electrochemical selective dual-oxidation approach that gives access toα-chlorosulfoxides from sulfides.This strategy presents broad substrate scope,high diastereoselectivity,and regioselectivity.The late-stage modification of amino acids and pharmaceutical derivatives further highlights the utility.Furthermore,detailed mechanistic studies reveal that the key success for this selective chemical transformation is the dual-oxidation process at the anode.This electrochemical dual-oxidation strategy may have wide universality;we anticipate diverse applications of this protocol across the many fields of chemistry.
基金supported by the National Science Fund for Distinguished Young Scholars of China (31625021)the Foundation for Innovative Research Groups of the National Natural Science Foundation of China (31821005)+1 种基金the State Key Program of National Natural Science Foundation of China (31530052)the Hainan University Startup Fund (KYQD(ZR)1866)。
文摘Genomic clustering of non-homologous genes for the biosynthesis of plant defensive compounds is an emerging theme, but insights into their formation and physiological function remain limited. Here we report the identification of a newly discovered hydroxycinnamoyl tyramine(HT) gene cluster in rice.This cluster contains a pyridoxamine 50-phosphate oxidase(Os PDX3) producing the cofactor pyridoxal50-phosphate(PLP), a PLP-dependent tyrosine decarboxylase(Os Ty DC1), and two duplicated hydroxycinnamoyl transferases(Os THT1 and Os THT2). These members were combined to represent an enzymological innovation gene cluster. Natural variation analysis showed that the abundance of the toxic tyramine intermediate of the gene cluster among different rice accessions is mainly determined by the coordinated transcription of Os Ty DC1 and Os THT1. Further pathogen incubation assays demonstrated that the end products of the HT gene cluster displayed enhanced resistance to the bacterial pathogen Xanthomonas oryzae pv. Oryzae(Xoo) and fungal pathogen Magnaporthe oryzae(M. oryzae), and the enhanced resistance is associated with the boost of phytoalexins and the activation of defense response. The unique presence of the HT gene cluster in Oryza AA genome, together with the enrichment of transposon elements within this gene cluster region, provides an evolutionary background to accelerate cluster member combinations. Our study not only discovered a gene cluster involved in the phenylpropanoid metabolism but also addressed the key aspects of gene cluster formation. In addition, our results provide a new metabolic pool for plant defense against pathogens.
