Electrochemically Enabled,Nickel‐Catalyzed Amination

Along with amide bond formation, Suzuki cross‐coupling, and reductive amination, the Buchwald–Hartwig–Ullmann‐type amination of aryl halides stands as one of the most employed reactions in modern medicinal chemistry. The work herein demonstrates the potential of utilizing electrochemistry to provide a complementary avenue to access such critical bonds using an inexpensive nickel catalyst under mild reaction conditions. Of note is the scalability, functional‐group tolerance, rapid rate, and the ability to employ a variety of aryl donors (Ar−Cl, Ar−Br, Ar−I, Ar−OTf), amine types (primary and secondary), and even alternative X−H donors (alcohols and amides).     

Palladium‐Catalyzed Fluoroarylation of gem‐Difluoroalkenes

A Pd‐catalyzed fluoroarylation of gem ‐difluoroalkenes with aryl halides is reported. By taking advantage of the in situ generated α‐CF₃‐benzylsilver intermediates derived from the nucleophilic addition of silver fluoride to gem ‐difluoroalkenes, this strategy bypasses the use of a strong base, thus enabling a mild and general synthetic method for ready access to non‐symmetric α,α‐disubstituted trifluoroethane derivatives.     

Buchwald–Hartwig Amination of Nitroarenes

The Buchwald–Hartwig amination of nitroarenes was achieved for the first time by using palladium catalysts bearing dialkyl(biaryl)phosphine ligands. These cross‐coupling reactions of nitroarenes with diarylamines, arylamines, and alkylamines afforded the corresponding substituted arylamines. A catalytic cycle involving the oxidative addition of the Ar−NO₂ bond to palladium(0) followed by nitrite/amine exchange is proposed based on a stoichiometric reaction.