ortho-Lithium/magnesium carboxylate-driven aromatic nucleophilic substitution reactions on unprotected naphthoic acids

J Org Chem. 2012 Jan 6;77(1):718-24. doi: 10.1021/jo202017z. Epub 2011 Dec 1.

Abstract

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 (CO(2)H) group. This novel nucleophilic aromatic substitution is presumed to proceed via a precoordination of the organometallic with the substrate, followed by an addition/elimination.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carboxylic Acids / chemistry*
  • Catalysis
  • Indicators and Reagents
  • Lithium / chemistry*
  • Magnesium / chemistry*
  • Molecular Structure
  • Naphthalenes / chemistry*
  • Organometallic Compounds

Substances

  • Carboxylic Acids
  • Indicators and Reagents
  • Naphthalenes
  • Organometallic Compounds
  • 1-naphthoic acid
  • Lithium
  • Magnesium
  • 2-naphthoic acid