METAL-CATALYZED ASYMMETRIC HETERO-DIELS-ALDER REACTIONS OF UNACTIVATED DIENES WITH GLYOXYLATES

The development of a catalytic asymmetric hetero-Diels-Alder methodolo gy for the reaction of unactivated dienes with glyoxylates is presente d. Several different asymmetric catalysts can be used, but copper-biso xazolines and aluminium-BINOL give the highest yield, and the best che mo- and enantioselectivities. The reaction course is dependent on seve ral factors such as the solvent and the anions coordinated to the cata lyst. The scope of the reaction is outlined by the total synthesis of a natural occurring actinidiolide.