Unified biomimetic assembly of voacalgine A and bipleiophylline via divergent oxidative couplings

Bipleiophylline is a highly complex monoterpene indole alkaloid composed of two pleiocarpamine units anchored on an aromatic spacer platform. The synthesis of bipleiophylline is considered as a mountain to climb by the organic chemistry community. Here, a unified oxidative coupling protocol between...

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Bibliographic Details
Published in:Nature chemistry 2017-08, Vol.9 (8), p.793-798
Main Authors: Lachkar, David, Denizot, Natacha, Bernadat, Guillaume, Ahamada, Kadiria, Beniddir, Mehdi A, Dumontet, Vincent, Gallard, Jean-François, Guillot, Régis, Leblanc, Karine, N'nang, Elvis Otogo, Turpin, Victor, Kouklovsky, Cyrille, Poupon, Erwan, Evanno, Laurent, Vincent, Guillaume
Format: Article
Language:English
Subjects:
Acids
Alkaloids
Alkaloids - chemistry
Biomimetics
Biosynthesis
Chemical Sciences
Chemistry
Couplings
Cycloaddition Reaction
Density Functional Theory
Derivatives
Dihydroxybenzoic acid
Hydroxybenzoates - chemistry
Indole Alkaloids - chemical synthesis
Indoles
Models, Chemical
Monoterpenes - chemical synthesis
NMR
Nuclear magnetic resonance
Organic chemistry
Oxidative Coupling
Oxides - chemistry
Scaffolds
Silver
Silver Compounds - chemistry
Stereoisomerism
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Summary:Bipleiophylline is a highly complex monoterpene indole alkaloid composed of two pleiocarpamine units anchored on an aromatic spacer platform. The synthesis of bipleiophylline is considered as a mountain to climb by the organic chemistry community. Here, a unified oxidative coupling protocol between indole derivatives and 2,3-dihydroxybenzoic acid, mediated by silver oxide, has been developed to produce the core of bipleiophylline. This method also allows the independent preparation of benzofuro[2,3-b]indolenine and isochromano[3,4-b]indolenine scaffolds, depending only on the nature of the aromatic platform used. The procedure has been applied to simple indole derivatives and to more challenging monoterpene indole alkaloids, thereby furnishing natural-product-like structures. The use of scarce pleiocarpamine as the starting indole allows the first syntheses of bipleiophylline and of its biosynthetic precursor, voacalgine A. The structure of the latter has been reassigned in the course of our investigations by 2D NMR and displays an isochromano[3,4-b]indolenine motif instead of a benzofuro[2,3-b]indolenine.
ISSN:1755-4330
1755-4349
DOI:10.1038/nchem.2735