Metal-free radical bicyclization/chloroalkylarylation of 1,6-enynes with chloroalkanes.

Free radical initiated bicyclization of 1,6-enynes with chloralkanes, is achieved selective activation of the C(sp)-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.

Photoinduced Tandem Cyanomethylation/Cyclization of Unsaturated Compounds: Access to Cyanomethylated 7- or 5-Membered -Heterocycles.

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 -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.

Nitro-Spirocyclization of Biaryl Ynones with -Butyl Nitrite: Access to NO-Substituted Spiro[5,5]trienones.

A metal/peroxide-free involved simple cascade 6--trig spirocyclization of -butyl nitrite with biaryl ynones has been finished, which resulted in various NO-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.

Preparation of alginate hydrogels through solution extrusion and the release behavior of different drugs.

Homogeneous alginate hydrogels were facilely fabricated through solution extrusion process. CaCO 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 Ca from CaCO particles induced by hydrolysis of GDL to reduce pH.