90-14-2Relevant articles and documents
Palladium-Catalyzed Decarbonylative Iodination of Aryl Carboxylic Acids Enabled by Ligand-Assisted Halide Exchange
Boehm, Philip,Cacherat, Bastien,Lee, Yong Ho,Martini, Tristano,Morandi, Bill
supporting information, p. 17211 - 17217 (2021/07/02)
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.
Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates
Klein, Philippe,Lechner, Vivien Denise,Schimmel, Tanja,Hintermann, Lukas
supporting information, p. 176 - 180 (2019/12/11)
The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C?X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C?O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C?X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl2–1,4-diazadiene catalyst system, in which 1,4-diazadiene (DAD) stands for diacetyl diimines, phenanthroline, bipyridine and related ligands. Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross-coupling or electrophilic substitution reactions.
Mechanism of Cu-catalyzed aryl boronic acid halodeboronation using electrophilic halogen: Development of a base-catalyzed iododeboronation for radiolabeling applications
Molloy, John J.,O'rourke, Kerry M.,Frias, Carolina P.,Sloan, Nikki L.,West, Matthew J.,Pimlott, Sally L.,Sutherland, Andrew,Watson, Allan J. B.
supporting information, p. 2488 - 2492 (2019/04/10)
An investigation into the mechanism of Cu-catalyzed aryl boronic acid halodeboronation using electrophilic halogen reagents is reported. Evidence is provided to show that this takes place via a boronate-driven ipso-substitution pathway and that Cu is not required for these processes to operate: General Lewis base catalysis is operational. This in turn allows the rational development of a general, simple, and effective base-catalyzed halodeboronation that is amenable to the preparation of 125I-labeled products for SPECT applications.