Recent Developments in Asymmetric Hetero-Diels-Alder Reactions of Dithioesters

Recent studies dealing with asymmetric thia-Diels-Alder reactions of dithioesters as heterodienophiles are described. A diastereoselective version involving new chiral dithioesters and the first example of a catalytic enantioselective version are described. The absolute stereochemistry of the cycloadducts was assigned based on an X-ray structure and chemical correlation. In order to rationalize the sense of the chiral induction observed experimentally, stereochemical models for Cu(II)/BOX/dithioester complexes are proposed.