Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.

The efficient preparation of nitrile-containing building blocks is of interest due to their utility as synthetic intermediates and their prevalence in pharmaceuticals.A s aresult, significant efforts have been made to develop methods to access these motifs whichrely on safer and non-toxicsources of CN.Herein, we report that 2-methyl-2-phenylpropanenitrile is an efficient, non-toxic,e lectrophilic CN source for the synthesis of nitrile-bearing quaternary centers by at hermodynamic transnitrilation and anion-relays trategy.T his one-pot process leads to nitrile products resulting from the gemdifunctionalization of alkyllithium reagents.

α-Aryl amines are prevalent in pharmaceutically active compounds and natural products. Herein, we describe a Ni-catalyzed protocol for their synthesis from readily available α-aryl ethers. While α-aryl ethers have been used as electrophiles in Ni-catalyzed C–C bond formations, their use in C–heteroatom bond formation is much less prevalent. Preliminary mechanistic insight suggests that oxidative addition is facilitated by an anionic ligand and that reductive elimination is a reversible process.

The efficient preparation of nitrile‐containing building blocks is of interest due to their utility as synthetic intermediates and their prevalence in pharmaceuticals. As a result, significant efforts have been made to develop methods to access these motifs which rely on safer and non‐toxic sources of CN. Herein, we report that 2‐methyl‐2‐phenylpropanenitrile is an efficient, non‐toxic, electrophilic CN source for the synthesis of nitrile‐bearing quaternary centers by a thermodynamic transnitrilation and anion‐relay strategy. This one‐pot process leads to nitrile products resulting from the gem‐difunctionalization of alkyl lithium reagents.

Quaternary α-(hetero)arylnitriles are desirable biologically relevant products, however the existing methods for their synthesis can be aselective or require the use of undesirable reagents, such as cyanide salts. Herein we...