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Palladium‐Catalyzed Decarbonylative Iodination of Aryl Carboxylic Acids Enabled by Ligand‐Assisted Halide Exchange
Author(s) -
Boehm Philip,
Martini Tristano,
Lee Yong Ho,
Cacherat Bastien,
Morandi Bill
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202103269
Subject(s) - chemistry , xantphos , aryl , iodide , palladium , catalysis , halogenation , phosphonium , aryl halide , reductive elimination , phosphonium salt , ligand (biochemistry) , nucleophile , iodobenzene , transmetalation , halogen , combinatorial chemistry , organic chemistry , biochemistry , alkyl , receptor
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.