Total Synthesis of Epoxyeujindole A

The total synthesis of epoxyeujindole
A, a structurally unusual
indole diterpenoid isolated from Eupenicillium javanicum, has been accomplished for the first time. The synthesis features
a late-stage cationic cyclization strategy, which took advantage of
an electron-rich olefinic substrate. The CDE ring system was assembled
via an enantioselective conjugate addition/alkylation, a Luche cyclization,
and a Nozaki–Hiyama–Kishi reaction. The heavily substituted
A ring was constructed through a Suzuki–Miyaura coupling and
a cationic cyclization, and the bridged fused B ring was formed through
a Prins reaction.