Total Synthesis of Repraesentin F and Configuration Reassignment by a Gold(I)-Catalyzed Cyclization Cascade.

The first total synthesis of repraesentin F has been accomplished by a highly diastereoselective gold(I)-catalyzed cyclization cascade as the key step. This cycloisomerization/Prins-type tandem transformation enabled direct access to the atypical tricyclic carbon skeleton of the natural product with the required syn/ anti/ syn ring fusion. This synthetic effort also allowed reassignment of the relative configuration of repraesentin F and determination of its absolute configuration.