Toward the second generation synthesis of aplyronine A: stereocontrolled assembly of the C1-C19 segment by using an asymmetric Nozaki-Hiyama-Kishi coupling.

An efficient synthesis of the C1−C19 segment of aplyronine A is described. Stereoselective construction of the C14−C15 (E)-trisubstituted double bond and the C13 stereocenter was achieved by using an asymmetric Nozaki−Hiyama−Kishi coupling.