Bronsted and Lewis Solid Acid Catalysts in the Valorization of Citronellal

Terpenes are valuable starting materials for the synthesis of molecules that are of interest to the flavor, fragrance, and pharmaceutical industries. However, most processes involve the use of mineral acids or homogeneous Lewis acid catalysts. Here, we report results obtained in the liquid-phase reaction of citronellal with anilines under heterogeneous catalysis conditions to give tricyclic compounds with interesting pharmacological activity. The terpenic aldehyde could be converted into octahydroacridines with a 92% yield through an intramolecular imino Diels-Alder reaction of the imine initially formed in the presence of an acidic clay such as Montmorillonite KSF. Selectivity to the desired product strongly depended on the acid sites distribution, with Bronsted acids favoring selectivity to octahydroacridine and formation of the cis isomer. Pure Lewis acids such as silica-alumina with a very low amount of alumina gave excellent results with electron-rich anilines like toluidine and p-anisidine. This protocol can be applied starting directly from essential oils such as kaffir lime oil, which has a high citronellal content.