Nickel-catalyzed cyclization of alkyne-nitriles with organoboronic acids involving anti-carbometalation of alkynes

A nickel-catalyzed regioselective addition/cyclization of o-(cyano)phenyl propargyl ethers with arylboronic acids has been developed, which provides an efficient protocol for the synthesis of highly functionalized 1-naphthylamines with wide structural diversity. The reaction is characterized by a regioselective and anti-addition of the arylboronic acids to the alkyne and subsequent facile nucleophilic addition of the resulting alkenylmetal to the tethered cyano group. Mechanistic studies reveal that a Ni(i) species might be involved in the catalytic process.