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Figure presented The ester-directed regioselective borylation of arenes catalyzed by a silica-supported monophosphine-Ir complex displayed a significantly broad substrate scope toward heteroaromatic compounds, including thiophene, pyrrole, furan, benzothiophene, benzofuran, indole, and carbazole derivatives. The regioselectivity is complementary to the selectivities observed in the heteroarene C-H borylation with the dtbpy-Ir catalyst system.

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To further enhance the anti-Aspergillus efficacy of our previously discovered antifungal lead compound 1, a series of benzoheterocycle analogues were designed, synthesized and evaluated for their in vitro antifungal activity. The most promising compounds 13s and 14a exhibited excellent antifungal activity against C. albicans, C. neoformans, A. fumigatus and fluconazole-resistant C. albicans strains, that was superior or comparable to those of the reference drugs fluconazole and voriconazole. GC?MS analyses suggested that the novel compound 13s might have a similar mechanism to fluconazole by inhibiting fungal lanosterol 14alpha-demethylase (CYP51). Furthermore, compounds 13s and 14a exhibited low inhibition profiles for various human cytochrome P450 isoforms as well as excellent blood plasma stability.

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(4-Chlorophenyl)-(1-oxo-1lambda4-benzo[b]thien-2-yl)methanone 2a was synthesized by oxidation of the corresponding benzo[b]thiophene derivative 2 with the oxidative system H2O2/TFA. This benzo[b]thiophene sulfoxide undergoes Michael-type nucleophilic addition of sulfur- and oxygen-containing nucleophiles either under basic conditions leading to 2,3-dihydro-3- substituted-benzo[b]-thiophene 1-oxides or in acidic media leading then to rearomatized 3-substituted-benzo[b]thiophenes. This method provides an easy two-step functionalization of 2-acyl-benzo[b]thiophene derivatives.

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We report a transition-metal-free synthesis of benzofurans from benzothiophenes and phenols that exploits the unique reactivity of sulfoxides. Through a sequence involving an interrupted Pummerer reaction and [3,3] sigmatropic rearrangement, phenols can be combined with readily accessible yet synthetically unexplored benzothiophene S-oxides to provide C3-arylated benzofuran products. The products from this approach can undergo subsequent functionalization to gain access to a range of important benzofuran derivatives.

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In vitro and ex vivo efficacies of four series of benzo[b]thiophene-2-carboxylic acid derivatives were studied against Mycobacterium tuberculosis H37Ra (MTB). Benzo[b]thiophenes were also tested in vitro against multidrug resistant Mycobacterium tuberculosis H37Ra (MDR-MTB), and 7b was found to be highly active against A- and D-MDR-MTB/MTB (MIC ranges 2.73-22.86 mug/mL). The activity of all benzo[b]thiophenes against M. bovis BCG (BCG) was also assessed grown under aerobic and under conditions of oxygen depletion. Compounds 8c and 8g showed significant activity with MICs of 0.60 and 0.61 mug/mL against dormant BCG. The low cytotoxicity and high selectivity index data against human cancer cell lines, HeLa, Panc-1, and THP-1 indicate the potential importance of the development of benzo[b]thiophene-based 1,3-diketones and flavones as lead candidates to treat mycobacterial infections. Molecular docking studies into the active site of DprE1 (Decaprenylphosphoryl-beta-d-ribose-2?-epimerase) enzyme revealed a similar binding mode to native ligand in the crystal structure thereby helping to understand the ligand-protein interactions and establish a structural basis for inhibition of MTB. In summary, its good activity in in vitro and ex vivo model, as well as its activity against multidrug-resistant M. tuberculosis H37Ra in a potentially latent state, makes 7b an attractive drug candidate for the therapy of tuberculosis.

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A convenient and efficient synthesis of 2-substituted benzo[b]thiophenes is described. This one-step reaction of alkylthiobenzaldehyde and activated electrophiles proceeded smoothly in toluene at 120 C with magnesium oxide as a catalyst. The target 2-substituted benzo[b]thiophenes are obtained in moderate yields and the side reaction is inhibited via azeotropic distillation. According to the experiments, a plausible mechanism is presented.

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Anodic fluorination of benzo[b]thiophene derivatives provided a complex mixture of di- and trifluorinated products. On the other hand, anodic fluorination of 3-oxo-2,3-dihydrobenzo[b]thiophene and methyl 3-oxo-2,3-dihydrobenzo[b]thiophene-2-carboxylate gave the corresponding monofluorinated products selectively in moderate yields. Anodic fluorination of methyl alpha-(2-cyanophenylthio)acetate followed by intramolecular cyclization provided 3-amino-2-fluorobenzo[b]thiophene in excellent yield. Georg Thieme Verlag Stuttgart · New York.

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A new synthetic method for dimethyl 2,3-dihydrobenzo[b]oxepine-2,4- dicarboxylates and methyl 2-(2- carbomethoxybenzo[b]furan-3-yl)propanoates by an intramolecular conjugate displacement reaction or an SN2 reaction of acetates of Morita-Baylis-Hillman adducts of methyl (2-formylphenoxy)acetates has been described.

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Treatment with acid of thiosalicylaldehyde- and salicylaldehyde-derived phenyl 3-phenyl-2-propenyl thioethers and ethers possessing latent oxonium ion functionality triggers simple or tandem cyclisation to give substituted dihydrobenzothiopyrans and dihydrobenzopyrans. Some derivatisation reactions of the products are described.

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Convenient silylborane precursors for introducing N,B-bidentate boryl ligands onto transition metals were designed, prepared, and employed in ready formation of irdium(IIl) complexes via Si-B oxidative addition. A practical, efficient catalytic ortho-borylation reaction of arenes with a broad range of directing groups was developed using an in situ generated catalyst from the silylborane preligand 3c and [IrCl(COD)]2.

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