Asymmetric Total Synthesis of the Complex Polycyclic Xanthone FD-594

A highly convergent approach was developed to achieve the first asymmetric and scalable total synthesis of FD-594, a complex polycyclic xanthone natural product from Streptomyces sp. TA-0256, in a longest linear sequence (LLS) of 20 steps. The trans-9,10-dihydrophenanthrene-9,10-diol fragment (B-C-D ring) was generated through a new strategy involving asymmetric dihydroxylation followed by Cu-mediated oxidative cyclization. Late-stage stereoselective glycosylation assembled the angular hexacyclic framework with a β-linked 2,6-dideoxy trisaccharide fragment.