Enantio‐ and Diastereoselective, Complete Hydrogenation of Benzofurans by Cascade Catalysis

We report an enantio‐ and diastereoselective, complete hydrogenation of multiply substituted benzofurans in a one‐pot cascade catalysis. The developed protocol facilitates the controlled installation of up to six new defined stereocenters and produces architecturally complex octahydrobenzofurans, prevalent in many bioactive molecules. A unique match of a chiral homogeneous ruthenium‐N‐heterocyclic carbene complex and an in situ activated rhodium catalyst from a complex precursor act in sequence to enable the presented process.