Formamides having 1-arylalkyl groups on nitrogen undergo an unprecedented dehydrogenative [4 + 2] cycloaddition reaction with alkynes via nickel/AlMe(3) cooperative catalysis to give highly substituted dihydropyridone derivatives in good yields. Notably, the transformation proceeds through double functionalization of C(sp(2))-H and C(sp(3))-H bonds in the formamides.

Cyanoformates and cyanoformamides are found to add across alkynes by nickel/Lewis acid (LA) cooperative catalysis to give beta-cyano-substituted acrylates and acrylamides, respectively, in highly stereoselective and regioselective manners. The resulting adducts serve as versatile synthetic building blocks through chemoselective transformations of the ester, amide, and cyano groups as demonstrated by the synthesis of typical structures of beta-cyano ester, beta-amino nitrile, gamma-lactam, disubstituted maleic anhydride, and gamma-aminobutyric acid. The related reactions of cyanoformate thioester and benzoyl cyanide, on the other hand, are found to add across alkynes with decarbonylation in the presence of a palladium/LA catalyst.

Nucleophilic substitution reactions of chlorosilanes with aryl Grignard reagents take place efficiently in the presence of copper(I) iodide to afford tetraorganosilanes.

The reactions of cyanoformates and cyanoformamides with alkynes are proceeding with high stereo‐ and regioselectivity.

Treatment of 2-methylene-1,3-dithiane 1-oxide with aryl iodides under palladium catalysis in the presence of potassium carbonate and tetrabutylammonium bromide leads to the Mizoroki–Heck arylation to yield 2-(arylmethylene)-1,3-dithiane 1-oxides in high yields.