A facile synthetic method for 4-aryl-4,5-dihydro­pyrrole-3-carboxylates is developed, with a rhodium-catalyzed ring expansion strategy from readily available 2-(azetidin-3-ylidene) acetates and aryl boronic acids. Mechanistic investigations suggest a novel domino “conjugate addition/N-directed α-C­(sp3)–H activation” process. The asymmetric catalytic synthesis of the 4-aryl-4,5-dihydro­pyrrole-3-carboxylate is realized by using QuinoxP* (91–97% ee). The synthetic utility of this protocol is demonstrated by the synthesis of 3,4-disubstituted or 2,3,4-trisubstituted pyrrolidines with excellent diastereoselectivities.

Domino conjugate addition/inert bond activation is a useful strategy to improve the efficiency of synthesis. We summarize the reports on the domino conjugate addition/inert bond activation, and its applications in the rhodium-catalyzed ring expansion and ring opening of azetidines.