Divergent Total Syntheses of (-)-Pseudocopsinine and (-)-Minovincinine.

The Journal of Organic Chemistry
Xianhuang ZengDale L Boger

Abstract

Herein, the first total syntheses of (-)-pseudocopsinine (1) and (-)-minovincine (3) from a common intermediate 8 are detailed, enlisting late-stage, hydrogen atom transfer (HAT)-mediated free radical bond formations (C20-C2 and C20-OH, respectively) that are unique to their core or structure. The approach to 1 features an Fe-mediated HAT reaction of the intermediate olefin 2, effecting a transannular C20-C2 free radical cyclization of a challenging substrate with formation of a strained [2.2.1] ring system and reaction of a poor acceptor tetrasubstituted alkene with a hindered secondary free radical to form a bond and quaternary center adjacent to another quaternary center. Central to the assemblage of their underlying Aspidosperma skeleton is a powerful [4 + 2]/[3 + 2] cycloaddition cascade of 1,3,4-oxadiazole 9, which affords the stereochemically rich and highly functionalized pentacyclic intermediate 8 as a single diastereomer in one step. The work extends the divergent total synthesis of four to now six different natural product alkaloid classes by distinguishing late stage key strategic bond formations within the underlying Aspidosperma core from the common intermediate 8. Together, the work represents use of strategic bo...Continue Reading

References

Sep 19, 2002·Journal of the American Chemical Society·Gordon D WilkieDale L Boger
Aug 10, 2006·Journal of the American Chemical Society·Gregory I ElliottDale L Boger
Dec 18, 2007·Journal of the American Chemical Society·Hayato IshikawaDale L Boger
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Jun 16, 2015·Tetrahedron·Kiyoun Lee, Dale L Boger
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Mar 18, 2016·Journal of the American Chemical Society·Carla ObradorsRyan A Shenvi
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Jun 26, 2018·Journal of the American Chemical Society·Zhaohong LuAng Li
Jul 24, 2018·Journal of the American Chemical Society·Isabel KerschgensRichmond Sarpong
Apr 27, 2019·Journal of the American Chemical Society·Dongyoung KimPatrick L Holland
Aug 20, 2020·Journal of the American Chemical Society·Guangpeng XuChao Li

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Citations

Feb 9, 2021·Journal of the American Chemical Society·Darius VrubliauskasChristopher D Vanderwal
Apr 7, 2021·Angewandte Chemie·Zhengyuan XinShuanhu Gao
Jul 30, 2021·Journal of the American Chemical Society·Xianhuang Zeng, Dale L Boger

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