Stereochemistry of intramolecular Diels–Alder furan (IMDAF) reactions of furyl-substituted chiral ethanolamides

Abstract

This paper describes the stereoselective outcome of the intramolecular Diels–Alder furan (IMDAF) reaction of substituted (2S,3S)-ethanolamides 9–13, which were synthesised from a furyl substituted cyanohydrin. The latter was obtained from 2-furaldehyde with high enantioselectivity by an oxynitrilase catalysed addition of hydrogen cyanide. The stereochemistry of the IMDAF products was shown to be dependent on the size of the ethanolamide substituents R. Small substituents (H, Me, CN) gave exclusively exo-cycloaddition, whereas more bulky ones (Ph, Et) gave both exo- and endo-addition, the larger phenyl substituent giving a high endo–exo-ratio.