Pyrrolo[1,2-a]indole chemistry. Reactions of a tridentate carbanion

Mitomycinoid Alkaloids: Mechanism of Action, Biosynthesis, Total Syntheses, and Synthetic Approaches

“…Previously attempted functionalization of 9H-pyrrolo[1,2-a]indole ( 338 ) [297] had remained relatively fruitless. [298] However, singlet oxygen oxidation in the presence of pyridine routinely gave 70% of 338 . Presumably the intermediate endoperoxide 337 was formed, and pyridine served to affect ring-opening and elimination to give 338 .…”

Synthesis and Applications of 9H‐Pyrrolo[1,2‐a]indole and 9H‐Pyrrolo[1,2‐a]indol‐9‐one Derivatives

“…It was noticed in this paper that the structure of this product was first incorrectly assigned to the 3 H ‐pyrrolo[1,2‐ a ]indole 10 . As subsequently demonstrated in numerous examples, it turned out that the initially 3 H ‐isomer formed after the intramolecular Wittig reaction isomerizes in situ to the most stable 9 H ‐isomer . This work is the logical extension of the methodologies used by the same team for the synthesis of 3 H ‐pyrrolizine, and 2 H ‐chromene derivatives .…”

synthesis of Dialkyl 9-Chloro-3H-Pyrrolo[1,2-A]Indole-2,3-Dicarboxylates Mediated by Vinylphosphonium Salts

“…3-Chloro-1H-indole-2-carboxaldehyde (2) was prepared by known method. 7 General procedure for synthesis of dialkyl 9-chloro-3Hpyrrolo [1,2-a]indole-2,3-dicarboxylate (3): 5,8 To a magnetically stirred solution of 3-chloro-1H-indole-2-carboxaldehyde (1mmol) and triphenylphosphine (1mmol) in dichloromethane (5 ml) was added, dropwise, dialkyl acetylenedicarboxylate (1mmol) in dichloromethane (2 ml) at -10 ºC over 10 min. The reaction mixture was then allowed to warm up to room temperature and stirred for 10 min.…”