Synthesis of a Chiral Auxiliary Family from Levoglucosenone and Evaluation in the Diels-Alder Reaction

A new family of chiral auxiliaries has been developed based on the lignocellulosic biomass pyrolysis product levoglucosenone. A promising single stereoisomer with an alcohol and p-stacking phenyl substituents was prepared in excellent yield in two steps from di-hydrolevoglucosenone without chromatography on >50 g scale. Acrylate esters prepared from the auxiliaries underwent diastereoselective Lewis acid promoted Diels-Alder reactions with cyclopentadiene (endo/exo 98: 2, endo d.r. up to 98: 2), dimethylbutadiene (d.r. 93: 7), and isoprene (d.r. > 98: 2)