Stereoselective Synthesis of Polysubstituted Dihydropyrroles via 1,5‐Addition and N‐1,4‐Addition Cascade

An unprecedented 1,5‐addition/N‐1,4‐addition cascade reaction is established via palladium hydride catalysis. A variety of polysubstituted dihydropyrrole skeletons are constructed in high yield and with exclusively >20:1 diastereoselectivity. An enantioselective protocol of this design is also developed to provide a novel access to enantioenriched dihydropyrroles.