Catalytic enantioselective total synthesis of (-)-platyphyllide and its structural revision

Abstract

The catalytic asymmetric total synthesis of platyphyllide has been accomplished. A key highly substituted cyclohexene derivative has been obtained by the catalytic asymmetric Diels-Alder reaction of Danishefsky diene with an electron-deficient alkene. The Diels-Alder adduct was converted to a protected cyclohexane-1,3-dione in chiral form by catalytic Ito-Saegusa oxidation. Although the reported structure of platyphyllide was successfully synthesized, the optical rotation was opposite that of the natural compound. The absolute configuration of natural (-)-platyphyllide is revised to be a (6S,7S)-enantiomer.