A novel copper-catalyzed direct trifluoromethylation of internal alkynes was developed, obtaining a series of trifluoromethylated coumarins in good yields. The cyclization was proposed to proceed via a radical mechanism under copper-catalyzed conditions with good functional group tolerance.
Recent developments in the photochemical carbon-carbon and carbon-heteroatom bond formation via photoinduced Ar-X bond dissociation are summarized. The transformations through the Ar-X bond dissociation enabled by photoenergy include nucleophilic substitution, arylation, alkylation, aminocarbonylation, aminosulfonylation and decarboxylative coupling reactions. Usually, the reactions undergo oneelectron-transfer couplings and aryl radicals or cations are involved as the key intermediates. Under ultraviolet irradiation or visible light, the reactions of aryl halides with reactive partners proceed smoothly under mild conditions. In some cases, the transformations can proceed without any metals or photo-redox catalysts. Moreover, the broad reaction scope is demonstrated with good functional group tolerance.Scheme 1 Cleavage of Ar-X bond under UV irradiation.Scheme 2 Formation of an aryl radical by a photoinduced redox process in the presence of a metal catalyst or organocatalyst.
A practical synthetic method for the generation of benzosultams via an intramolecular sp(2) C-H bond amination reaction of o-arylbenzenesulfonamides with PhI(OAc)2-I2 under metal-free conditions is developed. A broad range of substrates are tolerated under mild reaction conditions, affording bioactive benzosultams in good to excellent yields. The resulting benzothiazines could be conveniently transformed into their corresponding iodinated derivatives via electrophilic substitution reactions.
The present study aimed to investigate differentially expressed genes (DEGs) in whole blood (WB) obtained from patients with lumbar disc prolapse (LDP) and healthy volunteers. A total of 8 patients with LDP and 8 healthy volunteers were recruited. An Agilent SurePrint G3 human gene expression microarray 8×60 K was used to perform the microarray analyses. R was employed to identify DEGs, which were then subjected to bioinformatics analysis, including a Gene Ontology (GO) analysis, Kyoto Encyclopaedia of Genes and Genomes (KEGG) pathway analysis and protein-protein interaction (PPI) network analysis. DEGs in the degenerative annulus fibrosis (AF) and nucleus pulposus (NP) compared with non-degenerative tissues were also identified based on microarray data and the intersections of the three were assessed. Furthermore, reverse transcription-quantitative (RT-q)PCR was performed to confirm the aberrant expression levels of selected DEGs in the WB of all subjects. A total of 161 DEGs between LDP patients and the healthy controls were identified (128 upregulated and 33 downregulated). These DEGs were enriched in 293 biological process, 36 cellular component and 21 molecular function GO terms, as well as in 24 KEGG pathways. The PPI network contained 4 submodules, and Toll-like receptor 4 had the highest degree centrality. A total of 22 DEGs were common to the three groups of DEGs. The RT-qPCR assay confirmed that the expression levels of cytochrome P450 family 27 subfamily A member 1, superoxide dismutase 2, protein disulfide isomerase family A member 4, FKBP prolyl isomerase 11 and ectonucleotide pyrophosphatase/phosphodiesterase 4 were significantly different between the patient group and the volunteer group. In conclusion, several genes were identified as potential biomarkers in WB that should be further explored in future studies to determine their potential application in the clinical treatment and diagnosis of LDP, and the present bioinformatics analysis revealed several GO terms, KEGG pathways and submodules of the PPI network that may be involved in LDP, although the exact mechanisms remain elusive.
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