EnantioselectiveCascade Annulation of 1,2,3-Triazolesand Enals Enabled by Sequential Rhodium and Oxidative NHC CatalysisInvolving Cleavage, Migration, and Cyclization

The in situ-generated pyrrolin-3-ones serve as novel and versatile synthons, being employed as intermediates for the efficient production of pyrrole-fused lactones with high yield and excellent enantioselectivity. Herein, we introduce emerging rhodium and oxidative N-heterocyclic carbene relay catalysis that enables a highly enantioselective cascade annulation between easily available 1,2,3-triazoles and enals. In this proof-of-concept study, the in situ-generated pyrrolin-3-ones engage α,β-unsaturated acylazolium intermediates generated from enals via oxidative N-heterocyclic carbene catalysis.