[1,2]‐Phospha‐Brook Rearrangement‐Initiated Palladium‐Catalyzed Cyclization Reaction of Isocyanides and <i>o</i>‐Bromobenzaldehydes: Access to <scp>2<i>H</i></scp>‐Isoindole‐1‐carboxamides and <scp>2<i>H</i></scp>‐Isoindole‐1‐carbonitriles

Comprehensive Summary Herein, a [1,2]‐phospha‐Brook rearrangement‐initiated palladium‐catalyzed cyclization reaction for base‐controlled selective synthesis of 2 H ‐isoindole‐1‐carboxamide and 2 H ‐isoindole‐1‐carbonitrile derivatives has been described. This strategy features double isocyanide insertion, efficient bond combinations, simple operation and reaction conditions. Mechanistic studies show that the [1,2]‐phospha‐Brook rearrangement is the key step in this reaction. This protocol offers a novel and concise strategy for the synthesis of 2 H ‐isoindole derivatives.