Biosynthetically Inspired Syntheses of Secu'amamine A and Fluvirosaones A and B.
Angew Chem Int Ed Engl
; 59(17): 6894-6901, 2020 04 20.
Article
in En
| MEDLINE
| ID: mdl-32043725
ABSTRACT
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.
Key words
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Heterocyclic Compounds, Bridged-Ring
/
Biomimetics
/
Alkaloids
Language:
En
Journal:
Angew Chem Int Ed Engl
Year:
2020
Document type:
Article