Convergent and Efficient Total Synthesis of (+)-Heilonine Enabled by C-H Functionalizations.

We report a convergent and efficient total synthesis of the C- nor D- homo steroidal alkaloid (+)-heilonine with a hexacyclic ring system, nine stereocenters, and a trans -hydrindane moiety. Our synthesis features four selective C-H functionalizations to form key C-C bonds and stereocenters, a Stille carbonylative cross-coupling to connect the AB ring system with the DEF ring system, and a Nazarov cyclization to construct the five-membered C ring. These enabling transformations significantly reduced functional group manipulations and delivered (+)-heilonine in 11 or 13 longest linear sequence (LLS) steps.