Regiospecific ortho‐C−H Allylation of Benzoic Acids

A carboxylate‐directed ortho‐C−H functionalization has been developed and it allows the regiospecific introduction of allyl residues to benzoic acids. In the presence of a [Ru(p‐cymene)Cl2]2 and K3PO4, benzoic acids react with allyl acetates at only 50 °C to give the corresponding ortho‐allylbenzoic...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-10, Vol.57 (44), p.14580-14584
Main Authors: Trita, A. Stefania, Biafora, Agostino, Pichette Drapeau, Martin, Weber, Philip, Gooßen, Lukas J.
Format: Article
Language:English
Subjects:
Acetates
Acetic acid
Acids
Allyl compounds
allylation
Benzoic acid
carboxylic acids
Chemical reactions
Cymene
C−H activation
Decarboxylation
Migration
Potassium phosphate
Potassium phosphates
reaction mechanisms
ruthenium
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Summary:A carboxylate‐directed ortho‐C−H functionalization has been developed and it allows the regiospecific introduction of allyl residues to benzoic acids. In the presence of a [Ru(p‐cymene)Cl2]2 and K3PO4, benzoic acids react with allyl acetates at only 50 °C to give the corresponding ortho‐allylbenzoic acids. The protocol is generally applicable to both electron‐rich and electron‐poor benzoic acids in combination with linear and branched allyl acetates. The products can be further functionalized in situ, for example, by double‐bond migration, lactonization, or decarboxylation. Direct play: A carboxylate‐directed ortho‐allylation of benzoic acids is achieved in the presence of [Ru(p‐cymene)Cl2]2. The reaction is based on widely available, structurally diverse (hetero)aromatic carboxylate substrates and proceeds under remarkably mild reaction conditions. It is widely applicable to (hetero)aromatic benzoic acids and the products can be transformed in situ by acyloxylation, double‐bond isomerization, or protodecarboxylation.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201712520