A new approach to asymmetric synthesis of infectocaryone.

A useful and flexible strategy for synthesis of (-)- and (+)-infectocaryone from commercial sugars is developed. The key step of the synthesis is a new-type Diels-Alder reaction with good chemoselectivity and stereoselectivity, in which a mixture of alkene regioisomers in a dynamic equilibrium is employed as chiral dienophiles for the first time.