Premium
Biosynthetically Inspired Syntheses of Secu′amamine A and Fluvirosaones A and B
Author(s) -
Lee Sanghyeon,
Kang Gyumin,
Chung Garam,
Kim Dongwook,
Lee HeeYoon,
Han Sunkyu
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201916613
Subject(s) - enamine , chemistry , regioselectivity , biogenesis , cycloaddition , amine gas treating , derivative (finance) , stereochemistry , organic chemistry , catalysis , biochemistry , financial economics , economics , gene
Presented here is a concise synthesis of secu′amamine A, and fluvirosaones A and B from readily available allosecurinine and viroallosecurinine. The key C2‐enamine derivative of (viro)allosecurinine, the presumed biosynthetic precursors of these natural products, was accessed, for the first time, by a VO(acac) 2 ‐mediated regioselective Polonovski reaction. Formal hydration and 1,2‐amine shift of this pluripotent enamine compound afforded secu′amamine A. Formal oxidative [3+2] cycloaddition reaction between this enamine and TMS‐substituted methallyl iodide reagent paved the way to the precursors of fluvirosaones A and B. The relative stereochemistry at the C2 position of these advanced intermediates governs the fate of 1,2‐amine shift leading to fluvirosaones A and B. The syntheses of potential biosynthetic precursors and investigations of their chemical reactivities have provided insights regarding the biogenesis of these natural products.