- Competing Pathways in O-Arylations with Diaryliodonium Salts: Mechanistic Insights
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A mechanistic study of arylations of aliphatic alcohols and hydroxide with diaryliodonium salts, to give alkyl aryl ethers and diaryl ethers, has been performed using experimental techniques and DFT calculations. Aryne intermediates have been trapped, and additives to avoid by-product formation originating from arynes have been found. An alcohol oxidation pathway was observed in parallel to arylation; this is suggested to proceed by an intramolecular mechanism. Product formation pathways via ligand coupling and arynes have been compared, and 4-coordinated transition states were found to be favored in reactions with alcohols. Furthermore, a novel, direct nucleophilic substitution pathway has been identified in reactions with electron-deficient diaryliodonium salts.
- Stridfeldt, Elin,Lindstedt, Erik,Reitti, Marcus,Blid, Jan,Norrby, Per-Ola,Olofsson, Berit
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supporting information
p. 13249 - 13258
(2017/09/12)
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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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- Synthesis of copper nanoparticles supported on a microporous covalent triazine polymer: An efficient and reusable catalyst for O-arylation reaction
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Copper nanoparticles were supported on a microporous covalent triazine polymer prepared by the Friedel-Crafts reaction (Cu@MCTP-1). The resulting material was characterized by powder X-ray diffraction, thermogravimetric analysis, N2 adsorption-desorption isotherms at 77 K, transmission electron microscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma optical emission spectroscopy, and Cu particles with an average size of 3.0 nm and a BET total surface area of ca. 1002 m2 g-1 were obtained. Cu@MCTP-1 was evaluated as a heterogeneous catalyst for the Ullmann coupling of O-arylation over a series of aryl halides and phenols without employing expensive ligands or inert atmosphere, which produced an excellent yield of the corresponding diaryl ethers. The catalyst could be recovered by simple centrifugation and was reusable at least five times with only a slight decrease in catalytic activity.
- Puthiaraj, Pillaiyar,Ahn, Wha-Seung
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p. 1701 - 1709
(2016/04/05)
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- An in situ acidic carbon dioxide/glycol system for aerobic oxidative iodination of electron-rich aromatics catalyzed by Fe(NO3)3·9H2O
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An environmentally benign CO2/glycol reversible acidic system was developed for the iron(iii)-catalyzed aerobic oxidative iodination of electron-rich aromatics without the need for any conventional acid additive or organic solvent. Notably, moderate to high isolated yields (up to 97%) of the aryl iodides were attained with comparable regioselectivity when ferric nitrate nonahydrate was used as the catalyst with molecular iodine under 1 MPa of CO2.
- Ma, Ran,Huang, Cheng-Bin,Liu, An-Hua,Li, Xue-Dong,He, Liang-Nian
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p. 4308 - 4312
(2015/01/08)
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- Greener iodination of arenes using sulphated ceria-zirconia catalysts in polyethylene glycol
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An environmentally benign method for the selective monoiodination of diverse aromatic compounds has been developed using reusable sulphated ceria-zirconia under mild conditions. The protocol provides moderate to good yields and selectively introduces iodine at the para/ortho position in monosubstituted arenes. SO42-/Ce0.07Zr 0.93O2 was found to be the best choice for the synthesis of aryl iodides in high yield, presumably due to the maximum number of acid sites (4.23 mmol g-1) among the various compositions of the catalyst system.
- Kahandal, Sandeep S.,Kale, Sandip R.,Gawande, Manoj B.,Zboril, Radek,Varma, Rajender S.,Jayaram, Radha V.
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p. 6267 - 6274
(2014/01/23)
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- Triphenyltin chloride as a new source of phenyl group for C-heteroatom and C-C bond formation
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Ph3SnCl is introduced as a very suitable source of phenyl group for coupling with phenols, amines, and thiols in the presence of Cu(OAc)2 in Et3N at room temperature to give aryl ethers, amines, and arylthio ethers in high yields. In addition, the application of Ph3SnCl in the Stille coupling of aryl halides in the presence of Pd(0) catalyst in PEG 400 at 110C is discussed.
- Iranpoor, Nasser,Firouzabadi, Habib,Elham, Etemadi Davan,Rostami, Abed,Nematollahi, Arash
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p. 123 - 130
(2013/10/01)
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- Microwave-assisted synthesis of nonsymmetrical aryl ethers using nitro-arenes
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An efficient, microwave-assisted ligand-free, catalyst-free synthetic method for nonsymmetrical diaryl ethers has been developed by using nitroarenes. A variety of phenols and nitroarenes was scanned by using this method to produce nonsymmetrical aryl ethers. The newly developed method is an ecofriendly and cost-effective approach to synthesize nonsymmetrical aryl ethers.
- Sarkate, Aniket P.,Bahekar, Sushilkumar S.,Wadhai, Vijay M.,Ghandge, Ganesh N.,Wakte, Pravin S.,Shinde, Devanand B.
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p. 1513 - 1516
(2013/08/23)
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- Metal-free arylation of oxygen nucleophiles with diaryliodonium salts
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Phenols and carboxylic acids are efficiently arylated with diaryliodonium salts. The reaction conditions are mild, metal free, and avoid the use of halogenated solvents, additives, and excess reagents. The products are obtained in good-to-excellent yields after short reaction times. Steric hindrance is very well tolerated, both in the nucleophile and diaryliodonium salt. The scope includes ortho- and halo-substituted products, which are difficult to obtain by metal-catalyzed protocols. Many functional groups are tolerated, including carbonyl groups, heteroatoms, and alkenes. Unsymmetric salts can be chemoselectively utilized to obtain products with hitherto unreported levels of steric congestion. The arylation has been extended to sulfonic acids, which can be converted to sulfonate esters by two different approaches. With recent advances in efficient synthetic procedures for diaryliodonium salts the reagents are now inexpensive and readily available. The iodoarene byproduct formed from the iodonium reagent can be recovered quantitatively and used to regenerate the diaryliodonium salt, which improves the atom economy. Copyright
- Jalalian, Nazli,Petersen, Tue B.,Olofsson, Berit
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supporting information
p. 14140 - 14149,10
(2012/12/12)
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- Ligand-free highly effective iron/copper co-catalyzed formation of dimeric aryl ethers or sulfides
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Highly selective coupling of diiodoarenes with phenols or phenthiols can be performed by using a low-cost, benign character and readily available Fe/Cu catalytic system in the absence of ligands. It is noteworthy that the desired dimeric aryl ethers or sulfides could be obtained in high yields by coupling between diiodoarenes and phenols, or diphenols with aryl iodides. The Royal Society of Chemistry 2011.
- Qu, Xiaoming,Li, Tingyi,Zhu, Yan,Sun, Peng,Yang, Hailong,Mao, Jincheng
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supporting information; experimental part
p. 5043 - 5046
(2011/08/22)
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- Room temperature, metal-free synthesis of diaryl ethers with use of diaryliodonium salts
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A fast, high-yielding synthesis of diaryl ethers with use of mild and metal-free conditions has been developed. The scope includes bulky ortho-substituted diaryl ethers, which are difficult to obtain by metal-catalyzed protocols. Halo-substituents, racemization-prone amino acid derivatives, and heteroaromatics are also tolerated. The methodology is expected to be of high utility in the synthesis of complex molecules and in the pharmaceutical industry.
- Jalalian, Nazli,Ishikawa, Eloisa E.,Silva, Luiz F.,Olofsson, Berit
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supporting information; experimental part
p. 1552 - 1555
(2011/04/26)
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- Copper-catalyzed arene C-H bond cross-coupling
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A highly regioselective, one-pot sequential iodination-copper-catalyzed cross-coupling of arene C-H bonds has been developed affording an efficient method for biaryl synthesis.
- Do, Hien-Quang,Daugulis, Olafs
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supporting information; experimental part
p. 6433 - 6435
(2010/03/04)
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- Facile N-arylation of amines and sulfonamides and O-arylation of phenols and arenecarboxylic acids
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An efficient, transition-metal-free procedure for the N-arylation of amines, sulfonamides, and carbamates and O-arylation of phenols and carboxylic acids has been achieved by allowing these substrates to react with a variety of o-silylaryl inflates in the presence of CsF. Good to excellent yields of arylated products are obtained under very mild reaction conditions. This chemistry readily tolerates a variety of functional groups.
- Liu, Zhijian,Larock, Richard C.
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p. 3198 - 3209
(2007/10/03)
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- Facile O-Arylation of Phenols and Carboxylic Acids
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(Equation presented) A facile, transition-metal-free O-arylation procedure for phenols and aromatic carboxylic acids has been developed that affords good to excellent yields of arylated products under very mild reaction conditions. A methoxy-substituted aryl triflate affords O-arylated products in high yields with excellent regioselectivity. This chemistry tolerates a variety of functional groups.
- Liu, Zhijian,Larock, Richard C.
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- Direct and regioselective iodination and bromination of benzene, naphthalene and other activated aromatic compounds using iodine and bromine
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Direct and regioselective iodination and bromination of benzene, naphthalene and other activated aromatic compounds with iodine and bromine or their sodium salts proceed well in the presence of Fe(NO3) 3·1.5N2O4/charcoal in CH 2Cl2 at room temperature.
- Firouzabadi,Iranpoor,Shiri
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p. 8781 - 8785
(2007/10/03)
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- Halogenation of Aromatic Compounds by N-chloro-, N-bromo-, and N-iodosuccinimide
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An efficient and mild method for the halogenation of aromatic compounds using N-chloro-, N-bromo-, and N-iodosuccinimide in the presence of NH 4NO3 or FeCl3 in acetonitrile was developed.
- Tanemura, Kiyoshi,Suzuki, Tsuneo,Nishida, Yoko,Satsumabayashi, Koko,Horaguchi, Takaaki
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p. 932 - 933
(2007/10/03)
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- Synthetic use of poly[4-(diacetoxyiodo)styrene] for organic reactions
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Poly[4-(diacetoxyiodo)styrene] is sufficiently reactive for the iodination of aromatics, the oxidative 1,2-aryl migration of alkyl aryl ketones, the α-hydroxylation of ketones, and the oxidation of hydroquinones and sulfides similarly to (diacetoxyiodo)benzene. Here, those reactions with poly[4-(diacetoxyiodo)styrene] are very useful because of the simple operation; thus, filtration gives the crude products and recovered poly(4- iodostyrene), and then poly[4-(diacetoxyiodo)-styrene] can be regenerated by oxidation of the recovered poly(4-iodostyrene), which are reused for the same reactions.
- Togo, Hideo,Abe, Seiichiro,Nogami, Genki,Yokohama, Masataka
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p. 2351 - 2356
(2007/10/03)
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- Synthetic application of poly[styrene(iodoso diacetate)]
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Poly[styrene(iodoso diacetate)] is sufficiently reactive to effect the iodination of aromatics and oxidative 1,2-aryl migration of alkyl aryl ketones as (diacetoxyiodo)benzene, and can be regenerated and reused for the same reactions.
- Togo, Hideo,Nogami, Genki,Yokoyama, Masataka
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p. 534 - 536
(2007/10/03)
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- Room temperature regioselective iodination of aromatic ethers mediated by Selectfluor(TM) reagent F-TEDA-BF4
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Monosubstituted phenyl ethers were regioselectively iodinated with a mixture of iodine and F-TEDA in acetonitrile at room temperature at the para position, while 1-methoxy-4-substituted benzene derivatives were converted to 2-iodo products in high yield.
- Zupan, Marko,Iskra, Jernej,Stavber, Stojan
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p. 6305 - 6306
(2007/10/03)
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- Lower Nitrogen Oxide Species as Catalysts in a Convenient Procedure for the Iodination of Aromatic Compounds
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A simple method for the iodination of aromatic compounds, using I- as the iodine source and the O2 and catalytic amounts of NO+BF4- as the oxidant, is presented.The reactions are performed at 25 deg C in CF3COOH/CH2Cl2 or CF3COOH/CH3COOH mixtures and compounds with as different reactivities as the halobenzenes and 1-methoxynaphthalene can be iodinated in very good yields.A set of relative rates, isotope effects, and isomer distributions in accordance with the electrophilic action of an "I+" species are presented.The formation of "I+" is discussed in terms of possible outer-sphere and inner-sphere electron-transfer steps.Aromatic bromination and to a lesser extent chlorination can be performed by using similar methods.
- Radner, Finn
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p. 3548 - 3553
(2007/10/02)
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- Process for producing iodo-aromatic compounds
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In a process for producing an iodo-aromatic compound which comprises iodinating an aromatic compound having an electron-donating substituent bonded to the benzene ring with iodine in the presence of a solvent, the improvement wherein about 1/2 to about 10 moles, per mole of iodine added to the reaction system, of nitrogen dioxide (NO2) is added in the form of NO2 to the reaction system, and the reaction is carried out in the presence of nitrogen dioxide.
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- Ambident Reactivity of Anisole and p-Iodoanisole toward Phenylium Cations and Evidence for ipso-Attack in Cationic Phenylation
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The phenylation of p-iodoanisole from the thermolysis of benzenediazonium tetrafluoroborate affords, among other products, 4-methoxybiphenyl and 4-iododiphenyl ether, providing evidence for the occurrence of ipso-attack and attack on oxygen by C6H5+.In the case of anisole, the oxygen atom of the methoxy-substituent is also attacked by C6H5+ giving rise to diphenyl ether via the initial formation of diphenylmethyloxonium ion followed by intermolecular demethylation.We have demonstrated that no intramolecular rearrangement occurs with the oxonium ion.The results are consistent with a mechanism involving kinetically predominant C-phenylation of both substrates.Boron trifluoride (a Schiemann reaction product) promotes deiodination of p-iodoanisole and its phenylated isomers.This deiodination invalidates the conclusions drawn from isomeric distributions; therefore the presence of BF3 must be carafully controlled in a mechanistic study.
- Eustathopoulos, Helene,Court, Jean,Bonnier, Jane-Marie
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p. 803 - 808
(2007/10/02)
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