RESUMEN
Free radical initiated bicyclization of 1,6-enynes with chloralkanes, is achieved via selective activation of the C(sp3)-H bond of the chloralkane, resulting in diverse polychlorinated/chlorinated polyheterocycles. Two kinds of transformations and a scaled-up experiment were performed to test the synthetic importance of the organic chlorides. Finally, a range of radical inhibition operations and radical clock tests were explored to support the reaction process.
RESUMEN
A cyanomethylation/cyclization of aryl acetylenes/ethylenes with bromoacetonitrile was finished in a photopromoted condition, which offers an efficient and mild protocol for the preparation of cyanomethylated 7- or 5-membered N-heterocycles with good yields. Meanwhile, trichloroacetonitrile was also compatible with this radical pathway. In addition, a variety of single-crystal X-ray diffraction measurements, scaled-up operations to 1 mmol, functional group transformations of final products, light on/off experiments, and even radial inhibition studies were smoothly performed in this tandem system.
RESUMEN
A metal/peroxide-free involved simple cascade 6-exo-trig spirocyclization of tert-butyl nitrite with biaryl ynones has been finished, which resulted in various NO2-modified spiro[5,5]trienones with good regioselectivity/yields. A variety of scaled-up experiments, reduction/epoxidation operations, and mechanistic studies were performed to verify the merits and spirocyclization process of this radical system. Finally, the structure of the spirocycles was confirmed by single-crystal X-ray diffraction.
RESUMEN
Homogeneous alginate hydrogels were facilely fabricated through solution extrusion process. CaCO3 and D-glucono-δ-lactone (GDL) were used as the gelation agents. The slow gelation of alginate was realized by the in-situ release of Ca2+ from CaCO3 particles induced by hydrolysis of GDL to reduce pH. Slight gelation during the extrusion caused the enhanced strength of the alginate solutions, leading to the extrudability of the blends. This method enables to produce alginate hydrogels in a single step via extrusion, which is economically advantageous to conventional lab-scale preparation for mass production. Three different drugs, ibuprofen, acetaminophen, and methylthionine chloride, were used as model drugs to evaluate the drug release behavior of the alginate hydrogels. It was demonstrated that the drug release behavior was significantly adjusted by both the drug solubility and the ionic interaction between alginate and the drug molecule. It was shown that solution extrusion process is a feasible method to produce alginate-based drug delivery systems.
