A solvent-controlled switchable C-H alkenylation of 4-aryl-1H-pyrrole-3-carboxylates via a Pd(OAc)2 catalyzed oxidative Heck reaction was first realized. The corresponding C2 and C5 alkenylation products were obtained in good yields with high regioselectivities, respectively. The selective C5-alkenylation was successfully applied to the total synthesis of (±)-rhazinilam.
A 1,6‐addition arylation reaction of para‐quinone methides with α‐isocyanoacetamides and electron‐rich aromatic compounds under metal‐free conditions has been developed. BF3·Et2O plays two roles in the reaction: catalyzing the cyclization of α‐isocyanoacetamides to give oxazoles, and activating the para‐quinone methides to achieve the 1,6‐addition arylation process. The reaction shows good functional group tolerance, scalability, and regioselectivity. It is a consice protocol for the synthesis of diverse unsymmetrical triarylmethanes. Further transformation of the resulting triarylmethanes provides an efficient route to some functionalized molecules.
Sunflower Verticillium wilt is a widespread and destructive disease caused by the soilborne pathogen Verticillium dahliae. To better understand the process of infection and seed transmission of the fungus, sunflower roots were inoculated with a V. dahliae strain (VdBM9-6) labeled with green fluorescent protein (GFP) and monitored microscopically. After 24 to 96 h postinoculation (hpi), conidia germinated and developed into mycelium on root hairs, elongation zones, and caps of lateral roots. Mycelium colonized vascular bundles of lateral roots and taproots at 7 days postinoculation (dpi). At 10 weeks postinoculation (wpi), the epidermal cells, cortical tissues, and vascular elements of stem, petiole, and leaf veins were colonized by mycelium. By 12 wpi, strong GFP signals were detected not only on different tissues of inflorescence but also on testa of seed and a small fraction of pollen grains. A GFP signal was not observed on cotyledon tissues in the seed. Additionally, the colonization of V. dahliae on testa was also confirmed with MNP-10 selection medium, indicating that the testa of seed is the main carrier for the long distance transmission of sunflower yellow wilt.
Antibiotic 2,4-diacetylphloroglucinol (2,4-DAPG) produced by Pseudo11Wnas jl.uorescens CPF-IO and 2P24 is a principal factor enabling bacteria to suppress plant diseases caused by soilborne pathogens. In this study, a 2,4-DAPG biosynthesis locus phlACBDE cloned from strain CPF-IO was assembled into a mini-Tn5 transposon and introduced into the chromosome of P. jl.uorescens P32 (2,4-DAPG), CPF-IO and 2P24 to construct the 2,4-DAPG overproducing derivatives P32-38, CPFlO-9 and 2P24-48, respectively. All the transgenic strains showed an enhanced antibiosis capacity against plant microbial pathogens in vitro and two strains, P32-38 and CPFlO-9, provided significantly better protection against wheat take-all disease caused by Gaeumannomyces graminis var. tritici and tomato bacterial wilt caused by Ralstonia solanacearum in greenhouse. Compared to their parental strains, the 2,4-DAPG overproducing derivatives colonized to the same extent on the wheat tips in the autoclaved soil, but developed larger populations in natural soil. These results indicated that production of antibiotics 2,4-DAPG by biological control pseudomonads can contribute not only to their disease suppression capacities but also to the ecological competence in the resident microflora. Our research also suggests that it is a realistic approach to improve biocontrol capacity of P. fluorescens through the genetic modification of its antibiotic 2,4-DAPG production.
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