Abstract: | A highly enantioselective catalytic Diels–Alder (DA) cycloaddition of 2H‐pyran‐2,5‐diones (synthon of 5‐hydroxy‐2‐pyrones) has been developed with a Cinchona‐derived thiourea as the catalyst. The conditions were optimized by using 0.2 equiv. of the catalyst and 0.1 equiv. of formic acid in 2‐propanol at room temperature, which afforded the DA products in yields of up to 90% (exo/endo=5.5:1, 98% ee) with trans‐β‐nitrostyrene derivatives as the dienophiles. The structure/activity relationships of the bifunctional catalyst and the effects of the steric, electronic and hydrogen‐bonding properties of the dienophiles have been studied. |