Protecting Group-Dependent Synthesis of Densely Substituted Dihydropyrroles v/s Pyrroles via 5-Exo-trig Cascade Radical Cyclization to Alkynyl Vinylogous Carbamates

Densely substituted dihydropyrroles could be synthesized with excellent diastereoselectivity via 5-exo-trig cascade radical cyclization to alkynyl vinylogous carbamates. N-Alkyl/acyl protected alkynyl vinylogous carbamates upon radical cyclization using thiophenol gave substituted pyrroles as against dihydropyrroles, which were formed with N-sulfonyl protecting groups. This enabled a rare example wherein both dihydropyrrole and pyrrole rings are assembled in the same reaction. This strategy could be used for the synthesis of an unprecedented adjacent polyheterocyclic system having a furan-thiophene-pyrrole motif. When vinylogous carbamate is embedded in the isoindole moiety, a pyridoisoindole derivative was formed with excellent diastereoselectivity, instead of the expected pyrroloisoindole product.