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

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.