Nickel-catalyzed [2 + 2 + 2] benzannulation of alkynes: a new route to the synthesis of highly substituted naphthalenes.

The Ni(II)-catalyzed aromatic homologation of various directing groups with alkynes to afford highly substituted naphthalene products C-X bond cleavage followed by alkyne insertion and C-H activation is described. This reaction proceeded with a wide range of directing groups such as pyrazoles, imidazopyridines, benzoimidazothiazoles, thiazoles and triazoles with alkynes to afford highly substituted naphthalenes in moderate to good yields. This transformation is promoted by a simple, straightforward combination of a Ni(II)-complex, Zn dust and a base.