A direct diastereoselective synthesis approach of important 9H‐pyrrolo[1,2‐a]azepin‐9‐amines was established via base‐promoted [4+3] annulation between donor–acceptor reagents derived from 1H‐pyrrole‐2‐carbaldehydes and alkyl 2‐aroyl‐1‐chlorocyclopropanecarboxylates. This transition metal‐free domino reaction proceeded quickly under mild basic conditions, affording potentially bioactive azepine derivatives in moderate to high yields with high diastereoselectivities (up to >20:1).
