Ni-Catalyzed Reductive Fluoroalkylacylation of Alkynes for the Steroselective Synthesis of Fluoroalkylated Enones.

A Ni-catalyzed three-component reductive fluoroalkylacylation of alkynes with fluoroalkyl halides and acyl chlorides is presented. This dicarbofunctionalization provides an efficient method for the synthesis of fluoroalkyl-incorporated enones under mild conditions with high yields and excellent regioselectivity and stereoselectivity.

Base-promoted thioannulation of o-alkynyl oxime ethers with sodium sulfide for the general synthesis of isothiocoumarins.

A general and efficient strategy for the one-pot synthesis of isothiocoumarin-1-ones has been developed via the base-promoted 6-endo-dig thioannulation of o-alkynyl oxime ethers using the cheap and readily available Na2S as the sulfur source. Mechanistic studies disclosed that the reaction proceeded through two C-S bond formations, N-O bond cleavage and the final hydrolysis of imines.

Synthesis of Isoselenazoles and Isothiazoles from Demethoxylative Cycloaddition of Alkynyl Oxime Ethers.

A general method for the synthesis of isoselenazoles and isothiazoles has been developed by the base-promoted demethoxylative cycloaddition of alkynyl oxime ethers using the cheap and inactive Se powder and Na2S as selenium and sulfur sources. This transformation features the direct construction of N-, Se-, and S-containing heterocycles through the formation of N-Se/S and C-Se/S bonds in one-pot reactions with excellent functional group tolerance.