- Base- and Additive-Free Ir-Catalyzed ortho-Iodination of Benzoic Acids: Scope and Mechanistic Investigations
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A protocol for the C-H activation/iodination of benzoic acids catalyzed by a simple iridium complex has been developed. The method described in this paper allows the ortho-selective iodination of a variety of benzoic acids under extraordinarily mild conditions in the absence of any additive or base in 1,1,1,3,3,3-hexafluoroisopropanol as the solvent. The iridium catalyst used tolerates air and moisture, and selectively gives ortho-iodobenzoic acids with high conversions. Mechanistic investigations revealed that an Ir(III)/Ir(V) catalytic cycle operates, and that the unique properties of HFIP enables the C-H iodination using the carboxylic moiety as a directing group.
- Erbing, Elis,Sanz-Marco, Amparo,Vázquez-Romero, Ana,Malmberg, Jesper,Johansson, Magnus J.,Gómez-Bengoa, Enrique,Martín-Matute, Belén
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p. 920 - 925
(2018/02/14)
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- PdII-catalyzed monoselective ortho halogenation of C-H bonds assisted by counter cations: A complementary method to directed ortho lithiation
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(Chemical Equation Presented) When the counterion counts: The yield and selectivity of the title transformation of benzoic acid derivatives were improved greatly by using tetraalkyl ammonium salts as additives (see scheme; monoselectivity: 5:1-18:1). These effects are attributed to the influence of counter cations. The halogenated products are versatile intermediates for the construction of substituted aromatic compounds. DMF=N,N-dimethylformamide.
- Mei, Tian-Sheng,Giri, Ramesh,Maugel, Nathan,Yu, Jin-Quan
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supporting information; experimental part
p. 5215 - 5219
(2009/04/11)
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