Regiodivergent Synthesis of Penta-Substituted Pyrroles through a Cascade [3 + 2] Cyclization of C-Acylimines with Activated Alkynes and Aromatic Nucleophiles.

Highly robust one-pot, four-component cascade cyclization reaction of α-keto aldehydes, anilines, activated alkynes, and aromatic nucleophiles is developed to synthesize a diverse range of pharmaceutically important penta-substituted pyrroles. The reaction proceeds through the cascade cyclization of acylimines (in situ formed) with activated alkynes and aromatic nucleophiles such as indoles, pyrroles, and naphthols at room temperature under calcium(II) catalysis with high yields and broad substrate diversity.

Calcium-Catalyzed Stereoselective Tandem [4+2] and [3+2] Annulation Reaction for the Synthesis of Dihydropyrrolo[1,2-a]quinolines.

Calcium-catalyzed highly facile one-pot, A4 annulation of aldehyde, amine, alkene, and alkyne to form fused 4,5-dihydropyrrolo[1,2-a]quinolines with exclusive syn diastereoselectivity is reported. This selectivity arises from an inverse electron demand [4+2] aza-Diels-Alder cycloaddition, and the adduct further undergoes a formal [3+2] cyclization with activated alkynes. This diversity-oriented protocol is highly general and furnishes the dihydropyrrolo[1,2-a]quinoline derivatives with a broad substrate scope in good to excellent yields.