Asymmetric Intramolecular Aza-Michael Reaction in Desymmetrization Processes. Total Synthesis of Hippodamine and epi-Hippodamine

The use of chiral sulfinyl amines both as nucleophilic nitrogen sources and chiral inducers has been described for the first time in a desymmetrization-type process involving an intramolecular aza-Michael reaction. The resulting product was employed as an advanced intermediate in the total synthesis of the natural product hippodamine and epi-hippodamine, taking advantage of the special symmetry of these molecules. In addition, this is the first asymmetric total synthesis of epi-hippodamine.