Stereocontrol in Diels-Alder cycloaddition to unsaturated sugars: reactivities of acyclic seven-carbon trans dienophiles dervied from aldopentoles

Acyclic trans-2,3-unsaturated aldoheptonate derivatives (1–9) obtained from -aldopentoses by Witting chain-extension served as dienophiles for a detailed comparative study of their asymmetric Diels-Alder cycloaddition with cyclopentadiene. Cycloaddition under uncatalyzed thermal conditions gave mixtures of the four possible stereoisomeric norbornene adducts. The endo:exo ratios and the diastereofacial selectivities in the formation of the adducts were determined by NMR spectroscopy and by chemical transformations. The quantitative distribution of adducts as a function of stereochemistry of the dienophile is discussed.