No abstract

A new palladacyclic N-heterocyclic carbene precatalyst was designed by the combination of 1,3-bis(2,6diisopropylphenyl)acenaphthoimidazol-2-ylidene (AnIPr) with an achiral 2-naphthyl-4,4-dimethyloxazoline palladacyclic fragment. Applying this precatalyst enabled a general protocol for Pdcatalyzed C−N cross-coupling reactions of challenging five-or sixmembered ring heteroaryl chlorides and various heterocyclic amines. The desired aminated products, including commercial pharmaceuticals or key intermediates such as piribedil, cyprodinil, V600E BRAF inhibitor, tripelennamine, 517-β-hydroxysteroid dehydrogenase inhibitor, brexpiprazole, and sonidegib, were achieved in good to excellent yields (>61 examples, ≤99% yields).Heteroaryl carbon−nitrogen (C−N) bonds, ubiquitous structural units, are found in molecules of natural products, pharmaceuticals, agrochemicals, and functional materials (Scheme 1a). This ceaselessly inspires chemists to develop

In this study, a nickel‐catalyzed decarboxylative cyclization of isatoic anhydrides with carbodiimides was developed. This protocol realized the direct introduction of carbodiimides into heterocyclic compounds under an in situ generated Ni(0) complex. Synthetically, this methodology provides a simplified and secure new approach for the preparation of 2‐imino‐2,3‐dihydroquinazolin‐4(1H)‐ones. The control experiments and DFT theoretical calculations indicated that the Ni(0)‐catalyzed process is of central importance to the entire transformation.magnified image