Total synthesis of peloruside A via kinetic lactonization and relay RCM cyclization reactions (and identification of iso-peloruside A)

摘要

A convergent total synthesis of peloruside A (>1) is described. The key strategic features are a diastereoselective lactonization to generate a C5-C9 valerolactone from the C2-symmetric ketone >4, which comprises C1–C9 of >1, and a relay ring closing metathesis (RRCM) reaction to produce a dehydrovalerolactone >20, which embodies C13–C19. A new isomer of >1, the valerolactone iso-peloruside A (>iso-1), was identified.