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Abstract

Azepine ring is a prominent structural scaffold in biologically significant molecules. This study demonstrates a Ni(II)‐catalyzed alkyne functionalization/cyclization cascade reaction of alkyne‐tethered malononitriles, involving intermolecular regioselective arylation of the alkynes and desymmetrizing addition onto the nitrile group, to access azepine derivatives. This strategy introduces an all‐carbon quaternary stereocenter and an unprotected imine functionality simultaneously to the azepine scaffold, showing great promise for subsequent transformations. More details are discussed in the article by Liu et al. on page 873—878.image