Total Synthesis of (−)-Calyciphylline N

The total synthesis of the architecturally complex Daphni­phyllum alkaloid (−)-calyci­phylline N has been achieved. Highlights of the synthesis include a Et2AlCl-promoted, highly stereo­selective, susbtrate-controlled intramolecular Diels–Alder reaction, a transannular enolate alkylation, an effective Stille carbonylation/Nazarov cyclization sequence, and a high-risk diastereo­selective hydrogen­ation of a fully substituted conjugated diene ester.