Platinum-Catalyzed Intramolecular Alkylation of Indoles with Unactivated Olefins

Abstract

Reaction of 1-methy-2-(4-pentenyl)indole (1) with a catalytic amount of PtCl₂ (2 mol %) in dioxane that contained a trace of HCl (5 mol %) at 60 °C for 24 h led to the isolation of 4,9-dimethyl-2,3,4,9-tetrahydro-1H-carbazole (2) in 92% yield. Platinum-catalyzed cyclization of 2-(4-pentenyl)indoles tolerated substitution at each position of the 4-pentenyl chain. Furthermore, the protocol was applicable to the synthesis of tetrahydro-β-carbolinones and was effective for cyclization of unprotected indoles. 2-(3-Butenyl)indoles underwent platinum-catalyzed cyclization with exclusive 6-endo-trig regioselectivity. Mechanistic studies established a mechanism for the platinum-catalyzed cyclization of 2-alkenyl indoles involving nucleophilic attack of the indole on a platinum-complexed olefin.