The Daphniphyllum Alkaloids: Total Synthesis of (−)-Calyciphylline N

[Image: see text] Presented here is a full account on the development of a strategy culminating in the first total synthesis of the architecturally complex daphniphyllum alkaloid, (−)-calyciphylline N. Highlights of the approach include a highly diastereoselective, intramolecular Diels–Alder reaction of a silicon-tethered acrylate; an efficient Stille carbonylation of a sterically encumbered vinyl triflate; a one-pot Nazarov cyclization/proto-desilylation sequence; and the chemoselective hydrogenation of a fully substituted diene ester.