Catalyst-Controlled Chemodivergent Modification of Indoles with 2-Furylcarbinols: Piancatelli Reaction vs Cross-Dehydrative Coupling Reaction

A divergent synthetic strategy to functionalize the indole nucleus with readily available 2-furylcarbinols was developed. It was found that the 3-(4-oxo-2-cyclopentenyl)indoles were obtained in moderate to good yields (up to 89%) through Piancatelli reaction catalyzed by ZnCl2, whereas employment of Bronsted acid TFA afforded directly coupled product 3-(2-furyl)indoles in moderate to good yields (up to 87%) via the deprotonation–rearomatization route.