Asymmetric Defluoroallylation of 4-Trifluoromethylpyridines Enabled by Umpolung C-F Bond Activation.

Carbon-fluorine bond activation of the trifluoromethyl group represents an important approach to fluorine-containing molecules. While selective defluorinative functionalization reactions of CF3 -containing substrates have been achieved by invoking difluorocarbocation, difluorocarboradical, or difluoroorganometallic species as the key intermediates, the transformations via fluorocarbanion mechanism only achieved limited success. Furthermore, the enantioselective defluorinative transformation of the CF3 group remained a formidable challenge. Here we report a defluorinative functionalization reaction of 4-trifluoromethylpyridines involving difluoro(pyrid-4-yl)methyl anion as the key intermediate, which was developed based upon our previous studies on the N-boryl pyridyl anion chemistry. In particular, asymmetric defluoroallylation of 4-trifluoromethylpyridines and -pyrimidines could be achieved by using Ir-catalysis to forge a difluoroalkyl-substituted chiral center.

An umpolung approach to the hydroboration of pyridines: a novel and efficient synthesis of N-H 1,4-dihydropyridines.

The first inverse hydroboration of pyridine with a diboron(4) compound and a proton source has been realized under simple basic and catalyst-free conditions. This process consists of a formal boryl anion addition to pyridine, which produces an N-boryl pyridyl anion complex, and the subsequent protonation of the anion complex. This process enables a simple and efficient method for the synthesis of multi-substituted N-H 1,4-dihydropyridine (1,4-DHP) derivatives that are difficult to prepare using established methods. Furthermore, this method allows for facile preparation of 4-deuterated 1,4-DHPs from an easily accessible deuterium ion source. This inverse hydroboration reaction represents a new mode for pyridine functionalization.

[The expression of migration inhibitory factor in peripheral blood mononuclear cell and its correlation with disease activity in systemic lupus erythematosus].

OBJECTIVE: To investigate the change of macrophage migration inhibitory factor (MIF) mRNA expression in peripheral blood mononuclear cell (PBMC) and serum MIF and its correlation with disease active index in patients with systemic lupus erythematosus (SLE). METHODS: MIF mRNA expression of PBMC and serum MIF in patients with active and inactive SLE was measured by reverse transcriptase-polymerase chain reaction and enzyme-linked immunosorbent assay, respectively. The correlations of serum MIF with SLE disease active index, serum ds-DNA antibody, ANA, C3, C4 and IgG were examined. RESULTS: There was marked increase in MIF mRNA expression of PBMC and serum MIF in patients with SLE than that in normal volunteers (P < 0.01). Level of MIF in patients with active SLE was higher than that with inactive SLE (P < 0.01). There were significant correlation between the blood MIF concentration, MIF mRNA expression and SLE disease active index, ds-DNA antibody, C3, C4 and IgG, but no significant different was observed between the blood MIF and antinuclear antibody. CONCLUSIONS: MIF mRNA expression in PBMC and serum MIF concentration is significantly increased in patients with SLE and correlates with SLE disease activity. Serum MIF levels may be a useful parameter for monitoring disease active in patients with SLE.

Ti-Ge binary alloy system developed as potential dental materials.

As-cast Ti-xGe (x = 2, 5, 10, 20 wt %) binary alloys were produced in this work, and various experiments were carried out to investigate the microstructure, mechanical properties, in vitro electrochemical and immersion corrosion behaviors as well as cytotoxicity with as-cast pure Ti as control, aiming to study the feasibility of Ti-xGe alloy system as potential dental materials. The microstructure of Ti-xGe alloys changes from single α-Ti phase to α-Ti + Ti(5)Ge(3) precipitation phase with the increase of Ge content. Mechanical tests show that Ti-5Ge alloy has the best comprehensive mechanical properties. The corrosion behavior of Ti-xGe alloys in artificial saliva with different NaF and lactic acid addition at 37°C indicates that Ti-2Ge and Ti-5Ge alloys show better corrosion resistance to fluorine-containing solution. The cytotoxicity test indicates that Ti-xGe alloy extracts show no obvious reduction of cell viability to L-929 fibroblasts and MG-63 osteosarcoma cells, similar to pure Ti which is generally acknowledged to be biocompatible. Considering all these results, Ti-2Ge and Ti-5Ge alloys possess the optimal comprehensive performance and might be used as potential dental materials.