Total Synthesis of (−)-Conolutinine

The first enantioselective synthesis of (−)-conolutinine was achieved in 10 steps. The synthesis featured a catalytic asymmetric bromocyclization of tryptamine to forge the tricycle intermediate. Hydration of an alkene catalyzed by Co­(acac)₂ was also employed as a key step to diastereoselectively introduce the tertiary alcohol moiety. The absolute configuration of (−)-conolutinine was established to be (2<i>S</i>,5<i>aS</i>,8<i>aS</i>,13<i>aR</i>) based on this asymmetric total synthesis