A Catalytic Oxidative Quinone Heterofunctionalization Method: Synthesis of Strongylophorine‐26

The preparation of heteroatom‐substituted p‐quinones is ideally performed by direct addition of a nucleophile followed by in situ reoxidation. Albeit an appealing strategy, the reactivity of the p‐quinone moiety is not easily tamed and no broadly applicable method for heteroatom functionalization ex...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie 2018-07, Vol.130 (31), p.9953-9957
Main Authors: Yu, Wanwan, Hjerrild, Per, Jacobsen, Kristian M., Tobiesen, Henriette N., Clemmensen, Line, Poulsen, Thomas B.
Format: Article
Language:English
Subjects:
Catalysis
Catalysts
Chemical synthesis
Chemistry
Chinone
Cobalt
Cytotoxicity
Natural products
Naturstoffe
Nucleophiles
Oxidationen
Quinones
Reoxidation
Terpenoide
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The preparation of heteroatom‐substituted p‐quinones is ideally performed by direct addition of a nucleophile followed by in situ reoxidation. Albeit an appealing strategy, the reactivity of the p‐quinone moiety is not easily tamed and no broadly applicable method for heteroatom functionalization exists. Shown herein is that Co(OAc)2 and Mn(OAc)3⋅2 H2O act as powerful catalysts for oxidative p‐quinone functionalization with a collection of O, N, and S nucleophiles, using oxygen as the terminal oxidant. Preliminary mechanistic observations and the first synthesis of the cytotoxic natural product strongylophorine‐26 is presented. Kupplungen nach Belieben: Heteroatom‐funktionalisierte p‐Chinone sind häufig vorkommende Strukturmotive in biologisch aktiven Naturstoffen. Eine leistungsfähige katalytische Methode mit Übergangsmetallsalzen und molekularem Sauerstoff als Oxidationsmittel wurde entwickelt, die zur direkten Kupplung von p‐Chinonen an O‐, N‐ und S‐Nukleophile führt. Der Nutzen der Methode wird anhand der Synthese des Terpenoids Strongylophorin‐26 demonstriert.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201805580