Solvent effects in asymmetric hetero Diels-Alder and ene reactions

Abstract

The use of polar solvents such as nitromethane or 2-nitropropane leads to a significant improvement of the catalytic properties of a cationic copper-Lewis acid in the hetero Diels-Alder reaction of alkyl glyoxylates with dienes. The scope of a newly developed copper(II)-bisoxazoline catalyst for the hetero Diels-Alder reaction is demonstrated by the reaction of different dienes with alkyl glyoxylates in nitroalkane solvents with the formation of the hetero Diels-Alder adduct in high enantiomeric excess as the major product. The synthetic application of the reaction is exemplified by an improved synthesis of a highly interesting synthon for sesquiterpene lactones.