Abstract A readily accessible conjugate‐base‐stabilized carboxylic acid (CBSCA) catalyst facilitates highly enantioselective [4+2] cycloaddition reactions of salicylaldehyde‐derived acetals and cyclic enol ethers, resulting in the formation of polycyclic chromanes with oxygenation in the 2‐ and 4‐positions. Stereochemically more complex products can be obtained from racemic enol ethers. Spirocyclic products are also accessible.