Rapid Assembly of Functionalised Spirocyclic Indolines by Palladium-Catalysed Dearomatising Diallylation of Indoles with Allyl Acetate

Herein, we report the application of allyl acetate to the palladium‐catalysed dearomatising diallylation of indoles. The reaction can be carried out by using a readily available palladium catalyst at room temperature, and can be applied to a wide range of substituted indoles to provide access to the corresponding 3,3‐diallylindolinines. These compounds are versatile synthetic intermediates that readily undergo Ugi reactions or proline‐catalysed asymmetric Mannich reactions. Alternatively, acylation of the 3,3‐diallylindolinines with an acid chloride or a chloroformate, followed by treatment with aluminium chloride, enables 2,3‐diallylindoles to be prepared. By using ring‐closing metathesis, functionalised spirocyclic indoline scaffolds can be accessed from the Ugi products, and a dihydrocarbazole can be prepared from the corresponding 2,3‐diallylindole. Heterocycles: The application of allyl acetate to the palladium‐catalysed dearomatising diallylation of indoles is reported. The reaction can be carried out by using a readily available palladium catalyst at room temperature, enabling substituted indoles to be converted into 3,3‐diallylindolinines. These compounds are versatile synthetic intermediates that can be elaborated into a range of scaffolds including functionalised spirocyclic indolines and dihydrocarbazoles (see scheme).