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.

本文完整阐述了一条合成策略的开发历程，该策略首次实现了立体结构复杂的交让木生物碱（daphniphyllum alkaloid）(-)-calyciphylline N的全合成。该策略的亮点包括：硅桥连丙烯酸酯的高非对映选择性分子内狄尔斯-阿尔德（Diels–Alder）反应；空间位阻受阻的乙烯基三氟甲磺酸酯的高效施蒂勒羰基化反应；一锅法纳扎罗夫（Nazarov）环化/脱硅质子化串联序列；以及全取代二烯酯的化学选择性氢化反应。