Manganese(I)-Pincer Catalyzed α‑Alkylation of Sulfones by Alcohols

Sulfones are building blocks in organic synthesis and pharmaceutical chemistry. Direct α-alkylation of sulfones using alcohols with water as the sole byproduct is an efficient and promising method for their structural modifications. However, competitive reactions always exist in this transformation that influences the reaction selectivity. For example, in addition to the desired α-alkylation, Julia-type olefination and α-alkenylation are frequently observed, especially when benzyl alcohol derivatives were used as alkylation reagents. Herein, we report α-alkylation of sulfones using alcohols catalyzed by a pincer complex of earth-abundant manganese. The Mn-PNN-bipyridyl complex exhibited good performance in reaction selectivity. The amount of base also had an important influence on the smooth transformation. Aromatic and aliphatic alcohols are suitable alkylation reagents for sulfones at low metal catalyst loading (0.5 mol %), highlighting the practicality of the developed system

Chiral Selenide-Catalyzed Enantioselective Construction of Saturated Trifluoromethylthiolated Azaheterocycles

An indane-based, bifunctional, chiral selenide catalyst has been developed. The new catalyst is efficient for the enantioselective synthesis of saturated azaheterocycles possessing a trifluoromethylthio group. The desired products were obtained in good yields with high diastereo- and enantioselectivities

Diaryl Selenide Catalyzed Vicinal Trifluoro­methyl­thio­amination of Alkenes

An efficient approach to vicinal trifluoromethylthioamination of alkenes with a broad substrate scope catalyzed by electron-rich diaryl selenide has been developed. This intermolecular amination strategy was successfully applied to SCF₃-esterification of alkenes using weak acids as nucleophiles

Catalytic Enantioselective Aminative Difunctionalization of Alkenes

Enantioselective difunctionalization of alkenes offers a straightforward means for the rapid construction of enantioenriched complex molecules. Despite the tremendous efforts devoted to this field, enantioselective aminative difunctionalization remains a challenge, particularly through an electrophilic addition fashion. Herein, we report an unprecedented approach for the enantioselective aminative difunctionalization of alkenes via copper-catalyzed electrophilic addition with external azo compounds as nitrogen sources. A series of valuable cyclic hydrazine derivatives via either [3 + 2] cycloaddition or intramolecular cyclization have been achieved in high chemo-, regio-, enantio-, and diastereoselectivities. In this transformation, a wide range of functional groups, such as carboxylic acid, hydroxy, amide, sulfonamide, and aryl groups, could serve as nucleophiles. Importantly, a new cyano oxazoline chiral ligand was found to play a crucial role in the control of enantioselectivity

Designing New Magnesium Pincer Complexes for Catalytic Hydrogenation of Imines and <i>N</i>‑Heteroarenes: H₂ and N–H Activation by Metal–Ligand Cooperation as Key Steps

Utilization of main-group metals as alternatives to transition metals in homogeneous catalysis has become a hot research area in recent years. However, their application in catalytic hydrogenation is less common due to the difficulty in heterolytic cleavage of the H–H bond. Employing aromatization/de-aromatization metal–ligand cooperation (MLC) highly enhances the H2 activation process, offering an efficient approach for the hydrogenation of unsaturated molecules catalyzed by main-group metals. Herein, we report a series of new magnesium pincer complexes prepared using PNNH-type pincer ligands. The complexes were characterized by NMR and X-ray single-crystal diffraction. Reversible activation of H2 and N–H bonds by MLC employing these pincer complexes was developed. Using the new magnesium complexes, homogeneously catalyzed hydrogenation of aldimines and ketimines was achieved, affording secondary amines in excellent yields. Control experiments and DFT studies reveal that a pathway involving MLC is favorable for the hydrogenation reactions. Moreover, the efficient catalysis was extended to the selective hydrogenation of quinolines and other N-heteroarenes, presenting the first example of hydrogenation of N-heteroarenes homogeneously catalyzed by early main-group metal complexes. This study provides a new strategy for hydrogenation of CN bonds catalyzed by magnesium compounds and enriches the research of main-group metal catalysis

Diaryl Selenide Catalyzed Vicinal Trifluoro­methyl­thio­amination of Alkenes

An efficient approach to vicinal trifluoromethylthioamination of alkenes with a broad substrate scope catalyzed by electron-rich diaryl selenide has been developed. This intermolecular amination strategy was successfully applied to SCF₃-esterification of alkenes using weak acids as nucleophiles

Additional file 1 of The comorbid network characteristics of anxiety and depressive symptoms among Chinese college freshmen

Supplementary Material

Rapamycin enhanced the inhibiting effect of Dasatinib on cell proliferation and cell cycle progression in A549 cells.

<p>(A) The concentration-dependent effect of Rapamycin on the anticancer activity of Dasatinib in A549 cells. As detailed in the “<i>Methods</i>”, A549 cells were treated with vehicle control (0.1% DMSO) or Dasatinib (5, 10, 25, and 50 nM) in the presence and absence of Rapamycin (20, 50, and 100 nM). Viable cell numbers were analyzed at 72 h after the co-treatment. (B) Effects of Rapamycin on the temporal changes of Dasatinib-induced growth inhibition in A549 cells. Cells were treated with vehicle control (0.1% DMSO), Dasatinib (10 nM) with or without Rapamycin (100 nM). Cell numbers were measured at 0, 24, 48, 72, and 96 h after the treatment. (C) Effects of Dasatinib and Rapamycin on the cell cycle distribution. A549 cells were treated with Dasatinib (10 nM) or Rapamycin (100 nM) for 96 h and analyzed by flow cytometry after PI staining. Results are expressed as the average percentage of cells at G0/G1, S, and G2/M phase from three independent experiments. (D) Effects of Dasatinib and Rapamycin on the apoptosis in A549 cells. Cells were treated with Dasatinib (10 nM) or Rapamycin (100 nM) for 96 h and the apoptotic rates were determined by flow cytometry with Annexin-V and PI staining. Columns, mean of three determinations; bars, SD. * p < 0.05, ** p < 0.01.</p

Data_Sheet_1.XLSX

<p>Avian-like H5N1 canine influenza virus (CIV) causes severe respiratory infections in dogs. However, the mechanism underlying H5N1 CIV infection in dogs is unknown. The present study aimed to identify differentially expressed miRNAs and mRNAs in the lungs and trachea in H5N1 CIV-infected dogs through a next-generation sequencing-based method. Eighteen 40-day-old beagles were inoculated intranasally with CIV, A/canine/01/Guangdong/2013 (H5N1) at a tissue culture infectious dose 50 (TCID₅₀) of 10⁶, and lung and tracheal tissues were harvested at 3 and 7 d post-inoculation. The tissues were processed for miRNA and mRNA analysis. By means of miRNA-gene expression integrative negative analysis, we found miRNA–mRNA pairs. Lung and trachea tissues showed 138 and 135 negative miRNA–mRNA pairs, respectively. One hundred and twenty negative miRNA–mRNA pairs were found between the different tissues. In particular, pathways including the influenza A pathway, chemokine signaling pathways, and the PI3K-Akt signaling pathway were significantly enriched in all groups in responses to virus infection. Furthermore, dysregulation of miRNA and mRNA expression was observed in the respiratory tract of H5N1 CIV-infected dogs and notably, TLR4 (miR-146), NF-κB (miR-34c) and CCL5 (miR-335), CCL10 (miR-8908-5p), and GNGT2 (miR-122) were found to play important roles in regulating pathways that resist virus infection. To our knowledge, the present study is the first to analyze miRNA and mRNA expression in H5N1 CIV-infected dogs; furthermore, the present findings provide insights into the molecular mechanisms underlying influenza virus infection.</p

Phosphoric Acid Catalyzed <i>N</i>‑Addition/ <i>C</i>‑Addition Reaction of 3‑Vinyl Indoles with Pyrazole/Pyrazolone to Construct Pyrazole-Substituted 3‑(1-Heteroarylethyl)-indole Scaffolds

Developing a highly efficient atom-economic method for the preparation of 3-(1-heteroarylethyl)-indole scaffolds is of significant value in pharmaceutical and agricultural chemistry. Herein, a phosphoric acid-catalyzed N-addition reaction of 3-vinyl indoles with pyrazoles and C-addition reaction of 3-vinyl indoles with pyrazolones were developed. A series of pyrazole-substituted 3-(1-heteroarylethyl)-indole scaffolds were synthesized in excellent yields (up to 99% yield) under mild reaction conditions. A reasonable reaction mechanism was proposed to explain the experimental results