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 π-stacking phenyl substituents was prepared in excellent yield in two steps from di­hydrolevoglucosenone 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)