Pd-Catalyzed Boroperfluoroalkylation of Alkynes Opens a Route to One-Pot Reductive Carboperfluoroalkylation of Alkynes with Perfluoroalkyl and Aryl Iodides.

A three-component tandem Pd-catalyzed perfluoroalkylative borylation of terminal and internal alkynes is presented. On the basis of this methodology, the first reductive dicarbofunctionalization of alkynes with two electrophiles (perfluoroalkyl and aryl iodides) through a temperature-controlled sequence of iodoperfluoroalkylation-borylation coupling is developed. This regio- and stereoselective process is easily controllable by a temperature program, providing access to fluoroalkyl-substituted vinyl iodides, vinyl boronates, or olefins from the very same complex reaction mixture (four substrates, catalysts, base, and additives).