Abstract: | A very simple method was developed for the direct, palladium‐free catalytic α‐allylic alkylation of aldehydes. The direct organocatalytic intermolecular α‐allylic alkylation reaction was mediated by a simple combination of Brønsted acid and enamine catalysis which furnished α‐allylic alkylated aldehydes and cyclohexanone in high yields and chemoselectivities. The reaction conditions are mild and environmental friendly, the process is conducted under an atmosphere of air without the need for dried solvents, and water is the only side product of the allylic alkylation reaction. |