Chromium-mediated asymmetric synthesis of both enantiomers of acetoxytubipofuran

Article abstract of DOI:10.1021/ja029957n

Both enantiomers of acetoxytubipofuran were synthesized using enantioselective and diastereoselective dearomatization sequences starting from the benzaldehyde chromium tricarbonyl complex. Following aldol condensation, a sequence involving Pd-catalyzed allylic substitution was used in the synthesis of the (-)-enantiomer, whereas the (+)-enantiomer was reached via an Eschenmoser-Claisen rearrangement. Chiroptical data show that a revision of the previously assigned absolute configuration of the natural product is required. Copyright