Ortho-Lithium/Magnesium Carboxylate-Driven Aromatic Nucleophilic Substitution Reactions on Unprotected Naphthoic Acids

Regadia Aissaoui (1, 2) , Arnaud Nourry (1) , Ariane Coquel (1) , Thi Thanh Hà Dao (3) , Aïcha Derdour (2) , Jean-Jacques Helesbeux (3) , Olivier Duval (3) , Anne-Sophie Castanet (1) , Jacques Mortier (1)

1 UCO2M - Unité de chimie organique moléculaire et macromoléculaire
2 Laboratoire de Synthèse Organique Appliquée
3 SONAS - Substances d'Origine Naturelle et Analogues Structuraux

Substitution of an ortho-fluoro or methoxy group in 1- and 2-naphthoic acids furnishing substituted naphthoic acids occurs in good to excellent yields upon reaction with alkyl/vinyl/aryl organolithium and Grignard reagents, in the absence of a metal catalyst without the need to protect the carboxyl (CO2H) group. This novel nucleophilic aromatic substitution is presumed to proceed via a precoordination of the organometallic with the substrate, followed by an addition/elimination.

Domaines: Chimie organique

Regadia Aissaoui, Arnaud Nourry, Ariane Coquel, Thi Thanh Hà Dao, Aïcha Derdour, et al.. Ortho-Lithium/Magnesium Carboxylate-Driven Aromatic Nucleophilic Substitution Reactions on Unprotected Naphthoic Acids. Journal of Organic Chemistry, 2012, 77 (1), pp.718-724. ⟨10.1021/jo202017z⟩. ⟨hal-00711809⟩