- Decarboxylative Suzuki-Miyaura coupling of (hetero)aromatic carboxylic acids using iodine as the terminal oxidant
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A novel methodology for the decarboxylative Suzuki-Miyaura-type coupling has been established. This process uses iodine or a bromine source as both the decarboxylation mediator and the terminal oxidant, thus avoiding the need for stoichiometric amounts of transition metal salts previously required. Our new protocol allows for the construction of valuable biaryl architectures through the coupling of (hetero)aromatic carboxylic acids with arylboronic acids. The scope of this decarboxylative Suzuki reaction has been greatly diversified, allowing for previously inaccessible non-ortho-substituted aromatic acids to undergo this transformation. The procedure also benefits from low catalyst loadings and the absence of stoichiometric transition metal additives.
- Quibell, Jacob M.,Duan, Guojian,Perry, Gregory J.P.,Larrosa, Igor
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supporting information
p. 6445 - 6448
(2019/06/07)
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- One-Pot, Metal-Free Conversion of Anilines to Aryl Bromides and Iodides
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A metal-free synthesis of aryl bromides and iodides from anilines via halogen abstraction from bromotrichloromethane and diiodomethane is described. This one-pot reaction affords aryl halides from the corresponding anilines in moderate to excellent yields without isolation of diazonium salts. The transformation has short reaction times, a simple workup, and insensitivity to moisture and air and avoids excess halogenation. DFT calculations support a SRN1 mechanism. This method represents a convenient alternative to the classic Sandmeyer reaction.
- Leas, Derek A.,Dong, Yuxiang,Vennerstrom, Jonathan L.,Stack, Douglas E.
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supporting information
p. 2518 - 2521
(2017/05/24)
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- Method for synthesizing mono-aryl iodide or di-aryl iodide based on aromatic hydrocarbon carboxylic acid decarboxylic reaction
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The invention discloses a method for synthesizing mono-aryl iodide or di-aryl iodide based on aromatic hydrocarbon carboxylic acid decarboxylic reaction. The method is characterized in that under a protective atmosphere, carrying out one-pot reaction on a
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Paragraph 0097; 0098; 0099; 0100
(2017/07/23)
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- Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings
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Constructing products of high synthetic value from inexpensive and abundant starting materials is of great importance. Aryl iodides are essential building blocks for the synthesis of functional molecules, and efficient methods for their synthesis from chemical feedstocks are highly sought after. Here we report a low-cost decarboxylative iodination that occurs simply from readily available benzoic acids and I2. The reaction is scalable and the scope and robustness of the reaction is thoroughly examined. Mechanistic studies suggest that this reaction does not proceed via a radical mechanism, which is in contrast to classical Hunsdiecker-type decarboxylative halogenations. In addition, DFT studies allow comparisons to be made between our procedure and current transition-metal-catalyzed decarboxylations. The utility of this procedure is demonstrated in its application to oxidative cross-couplings of aromatics via decarboxylative/C-H or double decarboxylative activations that use I2 as the terminal oxidant. This strategy allows the preparation of biaryls previously inaccessible via decarboxylative methods and holds other advantages over existing decarboxylative oxidative couplings, as stoichiometric transition metals are avoided.
- Perry, Gregory J. P.,Quibell, Jacob M.,Panigrahi, Adyasha,Larrosa, Igor
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supporting information
p. 11527 - 11536
(2017/08/30)
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- Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions
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Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X = I, Br, Cl), and easy preparation of benzonitriles from decarboxylative cyanation of aryl carboxylic acids with nontoxic and low-cost K4Fe(CN)6 under an oxygen atmosphere for the first time.
- Fu, Zhengjiang,Li, Zhaojie,Song, Yuanyuan,Yang, Ruchun,Liu, Yanzhu,Cai, Hu
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p. 2794 - 2803
(2016/04/26)
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- Aryl diazonium nanomagnetic sulfate and potassium iodide: An iodination process
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A simple and efficient procedure for the synthesis of iodoarenes is developed which involves the sequential diazotization-iodination of aromatic amines with sodium nitrite, nanomagnetic supported sulfonic acid, and potassium iodide under solvent-free conditions at room temperature.
- Kolvari, Eskandar,Amoozadeh, Ali,Koukabi, Nadiya,Otokesh, Somayeh,Isari, Mohsen
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supporting information
p. 3648 - 3651
(2014/06/23)
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- Dihaloiodates(I): Synthesis with hydrogen peroxide and their halogenating activity
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Tetraalkylammonium and pyridinium dichloro- and dibromoiodates(I) were efficiently prepared from iodine and tetralkylammonium chloride or pyridine by oxidation with hydrogen peroxide in the presence of an equimolar amount of a hydrogen halide. Their halogenating activity was tested on 1,3-dimethoxybenzene and styrene as model substrates. The results show that ICl2 - salts acted as iodinating reagents, while IBr2 - salts brominated both substrates. 2012 Elsevier Ltd. All rights reserved.
- Bedra?, Leon,Iskra, Jernej
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p. 5555 - 5558
(2012/11/13)
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- Regioselective SNAr reactions of substituted difluorobenzene derivatives: practical synthesis of fluoroaryl ethers and substituted resorcinols
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In this Letter, we describe a practical and highly selective method for the preparation of fluoroaryl ethers and differentially substituted resorcinol derivatives. This synthetic strategy relies on a selective SNAr of substituted difluorobenzen
- Ouellet, Stéphane G.,Bernardi, Anna,Angelaud, Remy,O'Shea, Paul D.
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supporting information; experimental part
p. 3776 - 3779
(2009/10/11)
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- Practical electrochemical iodination of aromatic compounds
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A practical method for electrochemical iodination of aromatic compounds was developed. The method involves the generation of I+ by electrochemical oxidation of I2 in CH3CN using H 2SO4 as supporting electrolyte followed by the reaction with aromatic compounds. The para/ortho selectivity for the reaction of mono-substituted benzenes was significantly improved using dimethoxyethane as cosolvent in the second step. The reaction with highly reactive aromatic compounds led to the formation of significant amounts of diiodo compounds in a macrobatch reactor. This problem was solved by fast 1:1 mixing of I+ with an aromatic compound using a microflow system consisting of a T-shaped micromixer and a microtube reactor.
- Kataoka, Kazuhide,Hagiwara, Yuji,Midorikawa, Koji,Suga, Seiji,Yoshida, Jun-Ichi
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p. 1130 - 1136
(2013/01/03)
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- PROCESS FOR PRODUCING AROMATIC IODINE COMPOUND
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A process for producing an aromatic iodine compound. It has advantages of ease of handling and high safety. By the process, the reaction product having an excellent colour tone can be produced in a high yield. The process for aromatic iodine compound production is characterized by introducing an aromatic compound and an active iodizing agent into a flow-through type reactor equipped with a high-speed mixer to continuously replace hydrogen atoms of the aromatic nucleus of the aromatic compound with iodine atoms.
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- Selective monoiodination of aromatic compounds with electrochemically generated I+ using micromixing
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Selective monoiodination of aromatic compounds such as dimethoxybenzene has been successfully achieved with I+, which is generated by anodic oxidation of I2 in acetonitrile, using micromixing. The Royal Society of Chemistry 2006.
- Midorikawa, Koji,Suga, Seiji,Yoshida, Jun-Ichi
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p. 3794 - 3796
(2007/10/03)
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- PROCESS FOR PRODUCING AROMATIC IODINE COMPOUND
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A process for producing an aromatic iodine compound. It has advantages of ease of handling and high safety. By the process, the reaction product having an excellent color tone can be produced in a high yield. The process for aromatic iodine compound production is characterized by introducing an aromatic compound and an active iodizing agent into a flow-through type reactor equipped with a high-speed mixer to continuously replace hydrogen atoms of the aromatic nucleus of the aromatic compound with iodine atoms.
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Page/Page column 14-16; 20-21; 21-23; 25-26; 28-32
(2008/06/13)
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- Effective and regioselective iodination of arenes using iron(III) nitrate in the presence of tungstophosphoric acid
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An easy, cheap, and effective method for iodination of various aromatic compounds takes place with molecular iodine and iron nitrate nonahydrate as the oxidant in the presence of a catalytic amount of tungstophosphoric acid in dichloromethane, with good yield and high regioselectivity under very mild conditions.
- Jafarzadeh, Mohammad,Amani, Kamal,Nikpour, Farzad
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p. 1808 - 1811
(2007/10/03)
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- An Efficient, Catalytic, Aerobic, Oxidative Iodination of Arenes Using the H5PV2Mo10O40 Polyoxometalate as Catalyst
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Iodination of arenes was carried out by reacting 1 equiv of arene substrate with 0.5 equiv of iodine under an oxygen atmosphere with H 5PV2Mo10O40 as oxidation catalyst. The synthesis is an inherently waste-free method for the preparation of iodoarenes.
- Branytska, Olena V.,Neumann, Ronny
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p. 9510 - 9512
(2007/10/03)
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- Synthesis of Thyroid Hormone Analogues. Part 3. Iodonium Salt Approaches to SK&F L-94901
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The key step in the synthesis of L-3,5-dibromo-3'--thyronine, SK&F L-94901 (1), a novel, selective, and potent thyromimetic, is the formation of the hindered diaryl ether moiety.This paper describes an investigation into the formation of the required diaryl ether by copper-catalysed reaction both of symmetrical iodonium salts (2a) and (10) and mixed iodonium salts (2b-e) with protected dibromotyrosine (5).The importance of the counter-ion of the iodonium salt is discussed.This work is extended to a large-scale synthesis of SK&F L-94901 (1).
- Hickey, Deirdre M. B.,Leeson, Paul D.,Novelli, Riccardo,Shah, Virendra P.,Burpitt, Brian E.,et al.
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p. 3103 - 3112
(2007/10/02)
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