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

Abstract

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.

GRAPHICAL ABSTRACT

Keywords:

• Asymmetric hetero-Diels-Alder reaction
• thia-Diels-Alder reaction
• chiral dithioester
• Cu(II)/bis(oxazoline) complex
• stereochemical models

Acknowledgments

We acknowledge for the financial support the Ministère de la Recherche (grant to H.D.), the Centre de Recherche Universitaire Normand de Chimie Organique (CRUNCH), the Région Basse-Normandie, the CNRS, and the EU (FEDER funding). We thank Pr. A.-C. Gaumont (the leader of our research group) and Dr. I. Chataigner (Rouen), for helpful discussions.