Total Synthesis of RNA-Polymerase Inhibitor Ripostatin B and 15-Deoxyripostatin A

Keep me skipped: A highly convergent total synthesis of ripostatin B, an inhibitor of the bacterial RNA polymerase, is described. The key steps to construct and avoid isomerization of the skipped triene are a double Stille cross‐coupling reaction and a ring‐closing metathesis. Furthermore, 15‐deoxyripostatin A, a stable and conformationally locked analogue of ripostatin A (see scheme, 15‐OH group red), was prepared and tested in vivo.