Nickel‐Catalyzed Cascade C–H Alkynylation/Hydroamination of Free Benzylamines for the Synthesis of Substituted 1H‐Isoindoles Using a Transient Directing Group Strategy

Comprehensive Summary A nickel‐catalyzed cascade C(sp 2 )–H alkynylation/hydroamination of unprotected α‐substituted benzylamines is achieved using a transient directing group (TDG). The combination of a TDG with a nickel catalyst significantly improves the overall step‐ and atom‐economy. Studies have shown that the p ‐trifluoromethylbenzoic acid ligand is critical for achieving C(sp 2 )–H alkynylation and subsequent intramolecular hydroamination. This protocol provides a straightforward and efficient route for synthesizing substituted 1 H ‐isoindoles, featuring good substrate compatibility.