New chiral sulfoxide ligands in catalytic asymmetric Diels-Alder reactions: double acceleration by the chiralities of the sulfoxides and oxazolines

New chiral sulfoxide ligands which are useful for catalytic asymmetric Diel s-Alder reactions have been developed. The new ligands involve a chiral sul finyl function and a 1,3-oxazoline ring with an asymmetric carbon center, i n which the chiral sulfinyl group has been revealed to play a crucial role in achieving high enantioselectivity in asymmetric Diels-Alder reactions. A mong the Lewis acid catalysts employed, magnesium iodide provided the highe st chemical and stereochemical efficiency in the cycloaddition reactions. A mechanistic pathway for the asymmetric synthesis is proposed on the basis of the stereochemical outcomes obtained. (C) 2001 Elsevier Science Ltd. All rights reserved.