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.

本节详细阐述了开发一种策略的全过程，该策略最终实现了结构复杂的daphniophyllum生物碱（-）-calyciphylline N的首次完全合成。该策略的亮点包括：硅键合丙烯酸酯的高度对映选择性分子内Diels-Alder反应；对空间位阻较大的乙烯基三氟甲磺酸盐的高效Stille羰基化；一锅法Nazarov环化/原硅基消除反应序列；以及对完全取代的二烯酯的化学选择性加氢反应。