Expedient Introduction of β‐Methoxyacrylate Unit onto 3‐Substituted Indoles and Application of the Resulting Indole‐Dienes in Organocascade toward Indolino‐Polycyclics

An efficient methodology for introducing a β‐alkoxy acrylate unit onto the indolic C‐2 position of 3‐substituted indoles has been realized by oxidative radical alkylation of indoles with a xanthate bearing dialkyl acetal functionality and subsequent elimination of alcohol by treatment with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU). The indole‐dienes thus prepared are quite stable and can be stored at room temperature for several months without obvious deterioration. Next, the indole‐dienes were successfully applied in an asymmetric cascade reaction with propargyl aldehyde catalyzed by MacMillan’s imidazolidinone and trichloroacetic acid (TCA), affording tetracyclic spiroindolines or tricyclic hydrocarbazoles in good to excellent yields with excellent ees. The practicality of this cascade was demonstrated by a gram scale preparation of a tetracyclic spiroindoline product with as low as 1 mol% catalyst loading and further elaboration of this spiroindoline compound into valuable intermediates for alkaloid synthesis.