Asymmetric Total Synthesis of (−)‐Indicol by a Carbene Cyclization–Cycloaddition Cascade Strategy

The first total synthesis of a secodolastane, (-)-indicol, has been accomplished. The key reaction is a rhodium(II)-mediated carbene cyclization-cycloaddition cascade, by which the core bicyclo[5.4.0]undecane skeleton was assembled. In this one-pot reaction, a domino series of transformations resulting in the construction of three sigma bonds and three stereocenters was realized in good yield.