Palladium-Catalyzed Decarbonylative Iodination of Aryl Carboxylic Acids Enabled by Ligand-Assisted Halide Exchange

Philip Boehm, Tristano Martini, Yong Ho Lee, Bastien Cacherat, Bill Morandi

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

We report an efficient and broadly applicable palladium-catalyzed iodination of inexpensive and abundant aryl and vinyl carboxylic acids via in situ activation to the acid chloride and formation of a phosphonium salt. The use of 1-iodobutane as iodide source in combination with a base and a deoxychlorinating reagent gives access to a wide range of aryl and vinyl iodides under Pd/Xantphos catalysis, including complex drug-like scaffolds. Stoichiometric experiments and kinetic analysis suggest a unique mechanism involving C−P reductive elimination to form the Xantphos phosphonium chloride, which subsequently initiates an unusual halogen exchange by outer sphere nucleophilic substitution.

Original languageEnglish
Pages (from-to)17211-17217
Number of pages7
JournalAngewandte Chemie - International Edition
Volume60
Issue number31
DOIs
Publication statusPublished - 2021 Jul 26
Externally publishedYes

Keywords

  • iodination
  • ligand non-innocence
  • palladium
  • reaction mechanism
  • shuttle catalysis

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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