Synthesis of the antitumor antibiotic FR-66979: Dmitrienko oxidative expansion of a fully functional core structure

Article abstract of DOI:10.1016/0040-4039(96)01109-4

A stereocontrolled synthesis of the pentacyclic ring system 18, a projected advanced intermediate in the synthesis of FR-66979 (2), has been achieved. Key steps in the assembly of 18 include a copper(I) mediated cylization-oxidation of diazoketone 6 to mitosene 16 followed by an oxidative expansion of 16 to 18. The latter transformation proceeds via N-oxidation of diol 17.