- Metathesis-active ligands enable a catalytic functional group metathesis between aroyl chlorides and aryl iodides
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Current methods for functional group interconversion have, for the most part, relied on relatively strong driving forces which often require highly reactive reagents to generate irreversibly a desired product in high yield and selectivity. These approaches generally prevent the use of the same catalytic strategy to perform the reverse reaction. Here we describe a catalytic functional group metathesis approach to interconvert, under CO-free conditions, two synthetically important classes of electrophiles that are often employed in the preparation of pharmaceuticals and agrochemicals—aroyl chlorides (ArCOCl) and aryl iodides (ArI). Our reaction design relies on the implementation of a key reversible ligand C–P bond cleavage event, which enables a non-innocent, metathesis-active phosphine ligand to mediate a rapid aryl group transfer between the two different electrophiles. Beyond enabling a practical and safer approach to the interconversion of ArCOCl and ArI, this type of ligand non-innocence provides a blueprint for the development of a broad range of functional group metathesis reactions employing synthetically relevant aryl electrophiles.
- Lee, Yong Ho,Morandi, Bill
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p. 1016 - 1022
(2018/09/06)
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- Visible-Light-Induced Decarboxylative Iodination of Aromatic Carboxylic Acids
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A convenient, efficient and practical visible-light-induced decarboxylative iodination of aromatic carboxylic acids has been developed, and the corresponding aryl iodides were obtained in good yields. The method shows some advantages including the use of readily available aromatic carboxylic acids as the starting materials, simple and mild conditions, high efficiency, wide substrate scope and tolerance of various functional groups.
- Jiang, Min,Yang, Haijun,Jin, Yunhe,Ou, Lunyu,Fu, Hua
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supporting information
p. 1572 - 1577
(2018/06/26)
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- PROCESS FOR THE PREPARATION OF N-IODOAMIDES
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The present invention provides new stable crystalline N-iodoamides - 1-iodo- 3,5,5-trimethylhydantoin (1-ITMH) and 3-iodo-4,4-dimethyl-2-oxazolidinone (IDMO). The present invention further provides a process for the preparation of organic iodides using N-iodoamides of this invention and recovery of the amide co-products from waste water.
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Paragraph 00215-00216
(2015/05/26)
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- Cu-Catalyzed cascades to carbocycles: Union of diaryliodonium salts with alkenes or alkynes exploiting remote carbocations
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Copper-catalyzed cascade reactions between alkenes or alkynes and diaryliodonium salts form carbocyclic products in a single step. Arylation of the unsaturated functional group is proposed to form a carbocation intermediate that facilitates hydride shift pathways to translocate the positive charge to a remote position and enables ring formation via a Friedel-Crafts-type reaction.
- Zhang, Fengzhi,Das, Shoubhik,Walkinshaw, Andrew J.,Casitas, Alicia,Taylor, Michael,Suero, Marcos G.,Gaunt, Matthew J.
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supporting information
p. 8851 - 8854
(2014/07/08)
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- PROCESS FOR THE PREPARATION OF IODIDES
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This invention is directed to a process for the preparation of high yield alkyl or aryl iodide from its corresponding carboxylic acid using N-iodo amides.
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Page/Page column 34
(2012/01/05)
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- Mild preparation of haloarenes by ipso-substitution of arylboronic acids with N-halosuccinimides
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Aryl and heteroaryl boronic acids react with N-iodosuccinimide and N-bromosuccinimide to give the corresponding iodo-and bromo- arenes in good to excellent yields. The reaction is usually highly regioselective and yields only the ipso-substituted product. Esters of arylboronic acids react similarly, but less readily.
- Thiebes, Christoph,Prakash, G. K. Surya,Petasis, Nicos A.,Olah, George A.
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p. 141 - 142
(2007/10/03)
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- Silicon directed ipso-substitution of polymer bound arylsilanes: Preparation of biaryls via the Suzuki cross-coupling reaction
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A method for attaching haloarylsilanes to polymer support was developed. The polymer bound arylhalide were reacted with a variety of ArB(OH)2 under the Suzuki cross-coupling reaction conditions and the coupled resins were cleaved by different electrophiles to give ipso-substitution products in good yields.
- Han, Yongxin,Walker, Shawn D.,Young, Robert N.
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p. 2703 - 2706
(2007/10/03)
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- Simple anf Efficient Palladium-Catalyzed Carbonylation of Iodoxyarenes in Water under Mild Conditions
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Iodoxyarenes (ArIO2) readily react with CO (1 atm) in water, in the presence of Na2 (0.1percent) and Na2CO3 at 40-50 deg C, to give the corresponding carboxylic acids, ArCOOH, in 55-89percent isolated yield.Particulary attractive features of the reaction are that, unlike most iodoarenes, ArIO2 can be carbonylated in aqueous media without any organic solvents, due to their solubility in water and high reactivity.
- Grushin, Vladimir V.,Alper, Hovard
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p. 4794 - 4795
(2007/10/02)
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- Vapour-phase Chemistry of Arenes. Part 13. Reactivity and Selectivity in the Gas-phase Reactions of Hydroxyl Radicals with Monosubstituted Benzenes at 563 K
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The reactions of hydroxyl radicals with benzene derivates C6H5Z (Z = H, Me, F, Cl, Br, I, CF3, or CN) have been studied in a flow reactor at 563 K in nitrogen, using the thermolysis of ButOOH as a source of .OH.Under these conditions there are two product-forming pathways.The major one involves hydrogen abstraction to give aryl radicals ZC6H4. (II) as the first step; depending on Z, its displacement to form phenol may also occur.Relative rates for hydrogen abstraction were determined in competition experiments using side-chain hydrogen abstraction from added toluene as a reference.This resulted in the order (for Z =): 1,8(Me), 1.0(H), 0.47(F), 0.29(Cl), 0.34(CF3), 0.20(CN), consonant with the electrophilic nature of .OH.The site selectivity of hydrogen abstractions was determined by scavenging part of the aryl radicals (II) with iodine.A Hammett plot, using ? constants for meta and para positions, led to ρ -1.0.The features of hydrogen abstraction by .OH are discussed and compared with those for the analogous reaction of Cl.The formation of phenol was found to decrease in importance in the order F, Cl, Br, and I.This result is rationalized on a thermochemical kinetic basis.
- Mulder, Peter,Louw, Robert
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p. 1167 - 1174
(2007/10/02)
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- THE INVENTION OF RADICAL REACTIONS. PART XVI. RADICAL DECARBOXYLATIVE BROMINATION AND IODINATION OF AROMATIC ACIDS
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Thiohydroxamic esters of aromatic carboxylic acids undergo clean decarboxylative bromination or iodination on treatment with bromotrichloromethane, iodoform or diiodomethane in the presence of a radical initiator.
- Barton, Derek H.R.,Lacher, Brigitte,Zard, Samir Z.
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p. 4321 - 4328
(2007/10/02)
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- Polar Radicals. 17. On the Mechanism of Iodine Atom Transfer. A 9-I-2 Intermediate
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The atom-transfer reaction of iodine from an aryl iodide to a phenyl radical has been shown to proceed via a 9-I-2 ntermediate.The relative kinetics of the reactions of the intermediate were investigated by studying its mode of decomposition upon formation from the reduction of a series of unsymmetrically substituted diaryliodonium salts.The iodonium salts were reduced by the electron-transfer reactions with several reagents: di-tert-butyl nitroxide, sodium 2,6-di-tert-butylphenylate, and sodium phenylate.The reduction by electron transfer of the iodonium salts by the latter reaction gives high yields of diaryl ethers.The mechanism fo ether formation has been shown to proceed by two mechanistic pathways.For the diaryliodonium salts that have a p-cyano or p-nitro substituent, the ether is formed by a nucleophilic aromatic substitution; however, when the substituents were not strongly electron withdrawing, the mechanism resulting in ether formation involved electron transfer from the phenylate anion to the iodonium salt to form the phenoxy radical and a 9-I-2 intermediate.The intermediate decomposes to an aryl radical and an aryl iodide.The ether is formed from the efficient coupling of the aryl radical and the phenoxy radical.
- Tanner, Dennis D.,Reed, Darwin W.,Setiloane, B.P.
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p. 3917 - 3923
(2007/10/02)
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