- Direct Aromatic Iodination Using IF Prepared from I2 and F2
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IF, made directly from the corresponding elements, may be used without any catalyst as an electrophilic iodinating agent in its reactions with activated and deactivated aromatic rings.
- Rozen, Shlomo,Zamir, Dov,Menachem, Yinon,Brand, Michael
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Read Online
- Low-temperature reactions of dihalogenosilylenes, SiX2, with I2 or ICl in toluene yielding dihalogenoiodo(methylphenyl)silanes
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The gaseous silylenes, SiX2 (X = F, Cl, Br or I), have been condensed into solutions of I2 or ICl in toluene at -90°C to give a range of new compounds of formula SiX2I(C6H4Me), demonstrating the generality of a type of reaction of silylenes first observed with SiO. All the products were mixtures of ortho, meta and para isomers but with an uncommonly high proportion of the ortho isomer in some cases. As the same iodosilane derivatives were obtained using I2 or ICl as reagents, it is proposed that the reactions involve electrophilic attack of silylium ions, SiX2I+, on the arene.
- Church, Simon R.,Davies, Christopher G.,Luemen, Regine,Mounier, Pierre A.,Saint, Gavin,Timms, Peter L.
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Read Online
- Synthesis of biaryl compounds via Suzuki homocoupling reactions catalyzed by metal organic frameworks encapsulated with palladium nanoparticles
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Heterogeneous homocoupling reactions of phenylboronic acids were greatly accelerated via Suzuki homocoupling reactions. In this work, a tandem route was designed which firstly one part of phenylboronic acids reacted with iodine to form iodobenzenes, then another part of phenylboronic acids coupled with iodobenzenes to produce biaryl compounds. The tandem reaction were catalyzed by a bifunctional heterogeneous catalyst of metal organic frameworks encapsulated with palladium nanoparticles (Pd?MOFs). This strategy for forming symmetric C-C bond between benzene rings has obvious advantages such as high efficiency, easy separation, good recyclability and no addition of toxic halogenated benzene.
- Bao, Yan-Sai,Cui, Xin-Yu,Han, Zheng-Bo,Li, Xin,Tang, Hong,Yang, Ming,Zhang, Yu-Yang,Zhao, Kun,Zhou, Mei-Li
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- Alkali Metal Adducts of an Iron(0) Complex and Their Synergistic FLP-Type Activation of Aliphatic C-X Bonds
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We report the formation and full characterization of weak adducts between Li+ and Na+ cations and a neutral iron(0) complex, [Fe(CO)3(PMe3)2] (1), supported by weakly coordinating [BArF20] anions, [1·M][BArF20] (M = Li, Na). The adducts are found to synergistically activate aliphatic C-X bonds (X = F, Cl, Br, I, OMs, OTf), leading to the formation of iron(II) organyl compounds of the type [FeR(CO)3(PMe3)2][BArF20], of which several were isolated and fully characterized. Stoichiometric reactions with the resulting iron(II) organyl compounds show that this system can be utilized for homocoupling and cross-coupling reactions and the formation of new C-E bonds (E = C, H, O, N, S). Further, we utilize [1·M][BArF20] as a catalyst in a simple hydrodehalogenation reaction under mild conditions to showcase its potential use in catalytic reactions. Finally, the mechanism of activation is probed using DFT and kinetic experiments that reveal that the alkali metal and iron(0) center cooperate to cleave C-X via a mechanism closely related to intramolecular FLP activation.
- Tinnermann, Hendrik,Sung, Simon,Csókás, Dániel,Toh, Zhi Hao,Fraser, Craig,Young, Rowan D.
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supporting information
p. 10700 - 10708
(2021/07/31)
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- Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates
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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.
- Klein, Philippe,Lechner, Vivien Denise,Schimmel, Tanja,Hintermann, Lukas
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supporting information
p. 176 - 180
(2019/12/11)
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- Facile Access to Diverse Libraries of Internal Alkynes via Sequential Iododediazoniation/Decarboxylative Sonogashira Reaction in Imidazolium ILs without Ligand or Additive
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Convenient access to diverse libraries of internal alkynes via decarboxylative Sonogashira reaction of alkynyl-carboxylic acids with iodoarenes, employing imidazolium-ILs as solvent, along with piperidine-appended imidazolium [PAIM][NTf2] as task-specific basic IL is demonstrated, without the need for any ligand or additive. The feasibility to perform these reactions by sequential one-pot iododediazoniation/decarboxylative Sonogashira reaction is also shown, and the scope of the methods is underscored by providing 29 examples. The potential for recycling and reuse of the IL solvent is also examined.
- Prabhala, Pavankumar,Savanur, Hemantkumar M.,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
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supporting information
p. 2061 - 2064
(2019/03/07)
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- Nanolayered cobalt-molybdenum sulphides (Co-Mo-S) catalyse borrowing hydrogen C-S bond formation reactions of thiols or H2S with alcohols
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Nanolayered cobalt-molybdenum sulphide (Co-Mo-S) materials have been established as excellent catalysts for C-S bond construction. These catalysts allow for the preparation of a broad range of thioethers in good to excellent yields from structurally diverse thiols and readily available primary as well as secondary alcohols. Chemoselectivity in the presence of sensitive groups such as double bonds, nitriles, carboxylic esters and halogens has been demonstrated. It is also shown that the reaction takes place through a hydrogen-autotransfer (borrowing hydrogen) mechanism that involves Co-Mo-S-mediated dehydrogenation and hydrogenation reactions. A novel catalytic protocol based on the thioetherification of alcohols with hydrogen sulphide (H2S) to furnish symmetrical thioethers has also been developed using these earth-abundant metal-based sulphide catalysts.
- Corma, Avelino,Sorribes, Iván
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p. 3130 - 3142
(2019/03/13)
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- Mechanistic Interrogation of Co/Ni-Dual Catalyzed Hydroarylation
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Cobalt/nickel-dual catalyzed hydroarylation of terminal olefins with iodoarenes builds complexity from readily available starting materials, with a high preference for the Markovnikov (branched) product. Here, we advance a mechanistic model of this reaction through the use of reaction progress kinetic analysis (RPKA), radical clock experiments, and stoichiometric studies. Through exclusion of competing hypotheses, we conclude that the reaction proceeds through an unprecedented alkylcobalt to nickel direct transmetalation. Demonstration of catalytic alkene prefunctionalization, via spectroscopic observation of an organocobalt species, distinguishes this Csp2-Csp3 cross-coupling method from a conventional transmetalation process, which employs a stoichiometric organometallic nucleophile, and from a bimetallic oxidative addition of an organohalide across nickel, described by radical scission and subsequent alkyl radical capture at a second nickel center. A refined understanding of the reaction leads to an optimized hydroarylation procedure that excludes exogenous oxidant, demonstrating that the transmetalation is net redox neutral. Catalytic alkene prefunctionalization by cobalt and engagement with nickel catalytic cycles through direct transmetalation provides a new platform to merge these two rich areas of chemistry in preparatively useful ways.
- Shevick, Sophia L.,Obradors, Carla,Shenvi, Ryan A.
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supporting information
p. 12056 - 12068
(2018/09/27)
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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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- An efficient gram scale synthesis of aryl iodides from aryl diazofluoroborates in water under mild conditions
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Transition metal-free synthesis of synthetically valuable aryl iodides from aryl diazofluroborates in water under mild conditions has been described. Majority of synthesized aryl iodides are obtained in quantitative yields (>99%) under present reaction conditions. The structural effects due to the substituents present on aryl diazofluoroborates did not show any satisfactory effect on the yields of the aryl iodides. Hence, the methodology presented here was found to be adventitious for the quantitative production of synthetically valuable aryl iodides.
- Gholap, Somnath S.
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p. 594 - 599
(2018/06/26)
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- A general electrochemical strategy for the Sandmeyer reaction
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Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl3, CH2I2, CCl4, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot fashion. Furthermore, the practicality of this process was demonstrated in the multigram scale synthesis of aryl halides using highly inexpensive graphite as the electrode. A series of detailed mechanism studies have been performed, including radical clock and radical scavenger study, cyclic voltammetry analysis and in situ electron paramagnetic resonance (EPR) analysis.
- Liu, Qianyi,Sun, Beiqi,Liu, Zheng,Kao, Yi,Dong, Bo-Wei,Jiang, Shang-Da,Li, Feng,Liu, Guoquan,Yang, Yang,Mo, Fanyang
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p. 8731 - 8737
(2018/12/10)
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- Functional Group Transposition: A Palladium-Catalyzed Metathesis of Ar-X σ-Bonds and Acid Chloride Synthesis
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We describe the development of a new method to use palladium catalysis to form functionalized aromatics: via the metathesis of covalent σ-bonds between Ar-X fragments. This transformation demonstrates the dynamic nature of palladium-based oxidative addition/reductive elimination and offers a straightforward approach to incorporate reactive functional groups into aryl halides through exchange reactions. The reaction has been exploited to assemble acid chlorides without the use of high energy halogenating or toxic reagents and, instead, via the metathesis of aryl iodides with other acid chlorides.
- De La Higuera Macias, Maximiliano,Arndtsen, Bruce A.
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supporting information
p. 10140 - 10144
(2018/08/23)
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- Rapid Iododeboronation with and without Gold Catalysis: Application to Radiolabelling of Arenes
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Radiopharmaceuticals that incorporate radioactive iodine in combination with single-photon emission computed tomography imaging play a key role in nuclear medicine, with applications in drug development and disease diagnosis. Despite this importance, there are relatively few general methods for the incorporation of radioiodine into small molecules. This work reports a rapid air- and moisture-stable ipso-iododeboronation procedure that uses NIS in the non-toxic, green solvent dimethyl carbonate. The fast reaction and mild conditions of the gold-catalysed method led to the development of a highly efficient process for the radiolabelling of arenes, which constitutes the first example of an application of homogenous gold catalysis to selective radiosynthesis. This was exemplified by the efficient synthesis of radiolabelled meta-[125I]iodobenzylguanidine, a radiopharmaceutical that is used for the imaging and therapy of human norepinephrine transporter-expressing tumours.
- Webster, Stacey,O'Rourke, Kerry M.,Fletcher, Conor,Pimlott, Sally L.,Sutherland, Andrew,Lee, Ai-Lan
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supporting information
p. 937 - 943
(2017/12/26)
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- Metal-Free, Oxidant-Free, and Controllable Graphene Oxide Catalyzed Direct Iodination of Arenes and Ketones
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A direct, metal-free, and oxidant-free method for the graphene oxide (GO)-catalyzed iodination of arenes and ketones with iodine in a neutral medium was explored. This iodination protocol was performed by using a simple technique to avoid the use of external metal catalysts and oxidants and harsh acidic/basic reaction conditions. In addition, by this method the degree of iodination could be controlled, and the reaction was scalable and compatible with air. This strategy opens a new field for GO-catalyzed chemistry and provides an avenue for the convenient direct iodination of arenes and ketones.
- Zhang, Jingyu,Li, Shiguang,Deng, Guo-Jun,Gong, Hang
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p. 376 - 380
(2017/12/07)
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- Ultrasonically assisted halogenation of aromatic compounds using isoquinolinium bound hypervalent chromium and tetrabutylammonium halides in PEG-600 solutions under acid free and solvent-free conditions
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Isoquinolinium bound Cr(VI) reagents like isoquinolinium dichromate (IQDC) and isoquinolinium chlorochromate (IQCC) have been successfully accomplished as efficient reagents for oxidative halogenation of aromatic compounds using tetrabutylammonium halide (TBAX) as halogenating agents in aqueous polyethylene glycol (PEG-600) under acid free conditions. Tetrabutylammonium bromide (TBAB) has been used for bromination and tetrabutylammonium iodide (TBAI) for iodination. The halogenation reactions that occurred smoothly in 2 to 7 h under conventional conditions are accelerated magnificently under sonication with few minutes (25 to 70 min) of reaction time and fairly good yields. The reactions occurred at moderate temperature under mild and environmentally safe conditions with simple work up.
- Sambashiva Rao,Ramesh, Kola,Rajanna,Chakrvarthi
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p. 1892 - 1896
(2018/07/10)
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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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- Copper-catalyzed conversion of aryl and heteroaryl bromides into the corresponding iodide
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An efficient method for the synthesis of aryl and heteroaryl iodides is described in this study. The reactions of aryl and heteroaryl bromides with potassium iodide proceeded smoothly in the presence of a copper catalyst under mild reaction conditions to produce the corresponding iodides in satisfactory to excellent yields.
- Feng, Xiujuan,Li, Lingyu,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
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p. 129 - 132
(2016/07/06)
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- Method for preparing diazonium salt by utilizing micro-reactor
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The invention provides a method for preparing diazonium salt by utilizing a micro-reactor. The method comprises the following steps: firstly, preparing a nitrite solution and an organic amine into oil-water emulsion through a micro-mixer; enabling the oil-water emulsion to react with an introduced acid in a micro-channel to obtain the diazonium salt. The size of the salt formed by the contact of the oil-water emulsion and the acid is very small, and the salt can be consumed rapidly when reacting with nitrous acid, so that a pipeline is not blocked. The method provided by the invention is convenient and rapid to operate and short in reaction time; the defect that the diazonium salt is decomposed, caused by the fact that the temperature is too high, is avoided, and industrial production can be realized.
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Paragraph 0048; 0049
(2016/11/24)
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- Easy Access to Difluoromethylene-Containing Arene Analogues through Palladium-Catalysed C–H Olefination
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An efficient palladium-catalysed ortho-C–H olefination of α,α-difluorophenylacetic acid derivatives using 8-aminoquinoline as a bidentate directing group has been developed. A range of olefinated arenes can thus be synthesized in a concise way. This reaction provides an easy and straightforward route to a panel of difluoromethylated arene analogues in moderate to good yields, with a satisfactory tolerance of common functional groups. Transformation of the products into a variety of other difluoromethylene-containing compounds demonstrates the utility of this method.
- Shao, Changdong,Shi, Guangfa,Zhang, Yanghui
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supporting information
p. 5529 - 5538
(2016/11/25)
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- Isoquinolinium Dichromate and Chlorochromate as Efficient Catalysts for Oxidative Halogenation of Aromatic Compounds under Acid-Free Conditions
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Isoquinolinium dichromate and isoquinolinium chlorochromate were found as efficient catalysts to trigger oxidative bromination and iodination of aromatic hydrocarbons with KBr/KI and KHSO4 under acid-free conditions. Reaction times reduced highly significantly under sonication, followed by corresponding mono bromo derivatives in very good yield with high regioselectivity.
- Rao, A. Sambashiva,Rajanna,Reddy, K. Rajendar,Kulkarni, Subhash
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p. 832 - 837
(2016/02/12)
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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 00243-00244
(2015/05/26)
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- Practical and efficient ipso-iodination of arylboronic acids via KF/I2 system
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A facile and effective iododeboronation of variously substituted aryl and heteroarylboronic acids through activation and subsequent ipso-introduction of iodine is presented. The use of KF and I2 at 80 °C in 1,4-dioxane furnishes iodinated compounds in high yields.
- Tramutola, Francesco,Chiummiento, Lucia,Funicello, Maria,Lupattelli, Paolo
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p. 1122 - 1123
(2015/02/19)
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- An alternative to the Sandmeyer approach to aryl iodides
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Iodoarenes are important synthons for a wide range of organic transformations. Here we report a general strategy to prepare singly iodinated electron-rich aromatic compounds through the intermediacy of diaryliodonium salts. This process, which incorporates a phase separation that greatly simplifies product purification, is an attractive replacement for the Sandmeyer approach to iodoarenes that are otherwise difficult to access.
- Hu, Bao,Miller, William H.,Neumann, Kiel D.,Linstad, Ethan J.,DiMagno, Stephen G.
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p. 6394 - 6398
(2015/04/22)
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- Acetonitrile as a cyanating reagent: Cu-catalyzed cyanation of arenes
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A novel approach to the Cu-catalyzed cyanation of simple arenes using acetonitrile as an attractive cyano source has been documented. The C-H functionalization of arenes without directing groups involves a sequential iodination/cyanation to give the desired aromatic nitriles in good yields. A highly efficient Cu/TEMPO system for acetonitrile C-CN bond cleavage has been discovered. TEMPO is used as a cheap oxidant and enables the reaction to be catalytic in copper. Moreover, TEMPOCH2CN 6 has been identified as the active cyanating agent and shows high reactivity for forming the -CN moiety.
- Zhu, Yamin,Zhao, Mengdi,Lu, Wenkui,Li, Linyi,Shen, Zengming
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p. 2602 - 2605
(2015/06/16)
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- Metal-free iodination of arylboronic acids and the synthesis of biaryl derivatives
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A simple, general and efficient method is developed for the metal-free iodination of arylboronic acids. The protocol uses very cheap molecular iodine as the halide source and potassium carbonate as the base. The method is highly tolerant of various functional groups present in the substrates. Importantly, the iodination strategy can also be applied very effectively in the one-pot, two-step synthesis of biaryl derivatives. Georg Thieme Verlag Stuttgart New York.
- Niu, Liting,Zhang, Hao,Yang, Haijun,Fu, Hua
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supporting information
p. 995 - 1000
(2014/05/06)
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- Gold(I)-catalyzed iodination of arenes
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A wide variety of electron-rich arenes were efficiently converted into the corresponding iodinated compounds via a gold(I)-catalyzed reaction under mild conditions. Georg Thieme Verlag Stuttgart. New York.
- Leboeuf, David,Ciesielski, Jennifer,Frontier, Alison J.
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supporting information
p. 399 - 402
(2014/03/21)
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- Copper-catalyzed electrophilic carbofunctionalization of alkynes to highly functionalized tetrasubstituted alkenes
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Copper catalysts enable the electrophilic carbofunctionalization of alkynes with vinyl- and diaryliodonium triflates. The new process forms highly substituted alkenyl triflates from a range of alkynes via a pathway that is opposite to classical carbometalation. The alkenyl triflate products can be elaborated through cross-coupling reactions to generate synthetically useful tetrasubstituted alkenes
- Suero, Marcos G.,Bayle, Elliott D.,Collins, Beatrice S. L.,Gaunt, Matthew J.
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supporting information
p. 5332 - 5335
(2013/05/22)
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- Bronsted acidic ionic liquid accelerated halogenation of organic compounds with N-halosuccinimides (NXS)
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The Bronsted-Acidic ionic liquid 1-methyl-3-(4-sulfobutyl) imidazolium triflate [BMIM(SO3H)][OTf] was demonstrated to act efficiently as solvent and catalyst for the halogenation of activated organic compounds with N-halosuccinimides (NXS) under mild conditions with short reaction times. Methyl aryl ketones were converted into a-halo and a,a-dihaloketones, depending on the quantity of NXS used. Ketones with activated aromatic rings were selectively halogenated, however in some cases mixtures of a-halogenated ketone and ring-halogenated ketones were obtained. Activated aromatics were regioselectively ring halogenated to give mono- and dihalo-substituted products. The [BMIM(SO3H)][OTf] ionic liquid (IL-A) was successfully reused eight times in a representative monohalogenation reaction with no noticeable decrease in efficiency. An effective halogenation scale-up in this IL is also presented. The reactivity trend and the observed chemo- and regioselectiivities point to an ET process in these IL-promoted halofunctionalization reactions.
- Vrazic, Dejan,Jereb, Marjan,Laali, Kenneth K.,Stavber, Stojan
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- Synthesis of complex ortho-allyliodoarenes by employing the reductive iodonio-claisen rearrangement
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The reductive iodonio-Claisen rearrangement (RICR), involving complex aromatic λ3-iodanes and allyltrimethylsilane, was investigated. The RICR reaction of complex substituted aromatic hypervalent iodine (III) compounds and an allylmetal partner was conducted. The anionic oxy Cope rearrangement was found to be approximately 1010 to 1017 times faster than the neutral oxy Cope rearrangement due to weakening of the adjacent C-C bond by the oxygen anion. The results also indicate that the steric and electronic nature of the aromatic λ3-iodanes is the dominant factor influencing the [3,3]-sigmatropic rearrangement reaction. The removal of tert-butyl ether protecting group by using trifluroacetic acid in dichloromethane in the presence of triisopropylsilane gives the natural product broussin in 39% yield.
- Khatri, Hem Raj,Zhu, Jianglong
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p. 12232 - 12236
(2012/11/07)
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- Leaving group dependence of the rates of halogen-magnesium exchange reactions
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Relative reactivities and absolute rate constants of the reactions of haloarenes with i-PrMgCl?LiCl were investigated in THF at 0 °C. The rate of the halogen-magnesium exchange decreases in the series ArI > ArBr > ArCl (relative reactivities: 1011:106:1). Preliminary experiments show that the p-tolylsulfinyl group is exchanged slightly faster than iodide, while a tosyl group is exchanged at least 104 times more slowly than a bromide.
- Shi, Lei,Chu, Yuanyuan,Knochel, Paul,Mayr, Herbert
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experimental part
p. 2602 - 2605
(2012/08/08)
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- Synthesis and structure-activity relationship of 5-substituent-2(1H)- pyridone derivatives as anti-fibrosis agents
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Pyridone compounds, such as pirfenidone (PFD) and fluorofenidone (AKF-PD), are multi-target anti-fibrotic agents. Using PFD and AKF-PD as the leading compounds, two series of novel (5-substituent)-2(1H)-pyridone compounds were synthesized with the purpose of maintaining multi-targeting property and overcoming the drawbacks of fast metabolism. These derivatives demonstrated good proliferation inhibiting activity against NIH3T3 cells by MTT assay with AKF-PD as the positive control. Compound 5b exhibited a high potent of anti-fibrosis with a IC50 of 0.08 mmol/L about 34 times of AKF-PD. The SAR of pyridone derivatives as anti-fibrosis agents was also discussed.
- Chen, Jun,Lu, Miao-Miao,Liu, Bin,Chen, Zhuo,Li, Qian-Bin,Tao, Li-Jian,Hu, Gao-Yun
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scheme or table
p. 2300 - 2302
(2012/04/18)
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- Dichloroiodoisocyanuric acid: A new reagent for regioselective coiodination of alkenes and iodination of activated arenes
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Dichloroiodoisocyanuric acid was prepared in 93% by heating trichloroisocyanuric acid with 1.05 mol equiv. of iodine. This new reagent is very efficient for regioselective electrophilic iodination of activated arenes. Alkenes react with dichloroiodoisocyanuric acid in the presence of oxygenated nucleophiles (water, alcohols, and acetic acid), leading to the corresponding iodohydrins, β-iodoethers and β-iodoacetates with reaction times of less than one minute and with a high degree of regioselectivity. Enol ethers resulted in the regioselective formation of the corresponding iodine-dialkylacetals. Experimental results and DFT calculations showed that dichoroiodoisocyanuric acid is more reactive with unsaturated systems than triiodoisocyanuric acid.
- Da Silva Ribeiro, Rodrigo,Esteves, Pierre M.,De Mattos, Marcio C.S.
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experimental part
p. 228 - 235
(2012/05/05)
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- Potassium 4-iodylbenzenesulfonate: Preparation, structure, and application as a reagent for oxidative iodination of arenes
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A new hypervalent iodine(V) compound, potassium 4-iodylbenzenesulfonate, was prepared by the oxidation of 4-iodobenzensulfonic acid with Oxone in water. This potassium salt can be further converted into 4-iodylbenzenesulfonic acid by treatment with the acidic form of Amberlyst 15 in water. A single-crystal X-ray structure of potassium 4-iodylbenzenesulfonate revealed the presence of polymeric chains in the solid state due to a combination of numerous intra- and intermolecular interactions. Potassium 4-iodylbenzenesulfonate will likely find many practical applications as a thermally stable and water-soluble hypervalent iodine-based oxidant, particularly useful as a reagent for oxidative iodination of aromatic substrates. This reagent can be effectively recovered from the reaction mixture (92 % recovery) by treatment of the aqueous layer with Oxone at 60°C for 2 h, followed by filtration of the precipitate. A new hypervalent iodine(V) compound, potassium 4-iodylbenzenesulfonate, was prepared by oxidation of 4-iodobenzenesulfonic acid with Oxone in water. This new reagent promises many practical applications as a thermally stable, water-soluble and recyclable hypervalent iodine oxidant, particularly useful for oxidative iodination of aromatic substrates.
- Yusubov, Mekhman S.,Yusubova, Roza Y.,Nemykin, Victor N.,Maskaev, Andrey V.,Geraskina, Margarita R.,Kirschning, Andreas,Zhdankin, Viktor V.
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p. 5935 - 5942,8
(2020/09/02)
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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 35
(2012/01/05)
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- Hydrodehalogenation of aryl chlorides and aryl bromides using a microwave-assisted, copper-catalyzed concurrent tandem catalysis methodology
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A concurrent tandem catalytic methodology has been developed for the hydrodehalogenation of aryl bromides and aryl chlorides. The first step of the tandem catalytic cycle, halogen exchange, produced yields of 84-97% from aryl bromides using 5 mol % CuI catalyst, 10 mol % N,N′-dimethylcyclohexane-1, 2-diamine (1), and 2 equiv of NaI in acetonitrile under microwave radiation at 100 C in 0.5-1.5 h. The same reaction for aryl chlorides appeared to be equilibrium-limited after 1 hour at 200 C (yields of 5-44%). Both aryl bromides and aryl chlorides were hydrodehalogenated in 12-87% yield using 20 mol % CuI, 1.5 equiv of diamine 1, and 2 equiv of NaI in acetonitrile at 200 C after 1-2 h. Substrates with oxygen- or nitrogen-containing functional groups had substantially lower yields than hydrocarbon substrates. Deuterium labeling studies suggest that diamine 1 supplies the majority of the hydrogen for the hydrodehalogenation reaction, but solvent can also serve as a source. This article not subject to U.S. Copyright. Published 2011 by the American Chemical Society.
- Cannon, Kathleen A.,Geuther, Meagan E.,Kelly, Colin K.,Lin, Shirley,MacArthur, Amy H. Roy
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experimental part
p. 4067 - 4073
(2011/10/03)
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- General copper-catalyzed transformations of functional groups from arylboronic acids in water
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A simple and general copper-catalyzed method has been developed for transformations of various functional groups (i I, i N3, i SO2R, i OH, i NH2, and i NO 2) on aromatic rings from arylboronic acids in water under air. The protocol uses cheap and readily available inorganic salts (KI, NaN3, NaSO2R, NaOH, NaNO2) and aqueous ammonia as the functional-group sources, simple Cu2O/NH3 as the catalyst system, environmentally friendly water as the solvent, and oxygen in air as the oxidant. Importantly, the copper catalyst system in water was recyclable. This study should provide a useful strategy for interconversions of the functional groups on aromatic rings.
- Yang, Haijun,Li, Yong,Jiang, Min,Wang, Junmei,Fu, Hua
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experimental part
p. 5652 - 5660
(2011/06/23)
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- Copper-catalyzed halogenation of arylboronic acids
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In this Letter, a copper-catalyzed halogenation of arylboronic acids was described. This reaction tolerates a variety of functional groups, providing aromatic halides with good yields. It represents a facile and mild procedure to aryl halides.
- Zhang, Guangyou,Lv, Guanglei,Li, Liping,Chen, Fan,Cheng, Jiang
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experimental part
p. 1993 - 1995
(2011/04/25)
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- Triolborates: water-soluble complexes of arylboronic acids as precursors to iodoarenes
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A facile synthesis of aryl and heteroaryl iodides from water-soluble complexes of aryl- and heteroarylboronic acids has been developed.
- Akula, Murthy R.,Yao, Min-Liang,Kabalka, George W.
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experimental part
p. 1170 - 1171
(2010/04/23)
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- METHOD OF PRODUCING IODIZING AGENT, AND METHOD OF PRODUCING AROMATIC IODINE COMPOUND
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A method of the present invention, for producing an iodizing agent, includes the step of electrolyzing iodine molecules in a solution by using an acid as a supporting electrolyte. This realizes (i) a method of producing an iodine cation suitable for use as an iodizing agent that does not require a sophisticated separation operation after iodizing reaction is completed, and (ii) an electrolyte used in the method. Further, a method of the present invention, for producing an aromatic iodine compound, includes the step of causing an iodizing agent, and an aromatic compound whose nucleus has one or more substituent groups and two or more hydrogen atoms, to react with each other under the presence of a certain ether compound. This realizes such a method of producing an aromatic iodine compound that position selectivity in iodizing reaction of an aromatic compound is improved.
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Page/Page column 15-16
(2010/05/13)
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- Mild arming and derivatization of natural products via an In(OTf) 3-catalyzed arene iodination
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Figure presented Iodination of arene-containing natural products employing N-iodosuccinimide catalyzed by In(OTf)3 at ambient temperature is reported as a versatile and mild method for natural product derivatization amenable to small scale. This process facilitates natural product derivatization of arene moieties for SAR studies, homo- and heterodimerization of natural products, and also conjugation with reporters such as biotin via subsequent metal-mediated coupling reactions.
- Zhou, Cong-Ying,Li, Jing,Peddibhotla, Satyamaheshwar,Romo, Daniel
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supporting information; experimental part
p. 2104 - 2107
(2010/09/15)
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- A one-pot method for the iodination of aryl amines via stable aryl diazonium silica sulfates under solvent-free conditions
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A convenient and rapid one-pot method for the synthesis of iodoarenes is developed which involves the sequential diazotization-iodination of aromatic amines with sodium nitrite, silica sulfuric acid and potassium iodide under solvent-free conditions at room temperature. Various aromatic amines possessing electron-withdrawing groups or electron-donating groups are converted into the corresponding aryl iodides in good yields. Georg Thieme Verlag Stuttgart.
- Zarei, Amin,Hajipour, Abdol R.,Khazdoozd, Leila
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experimental part
p. 941 - 944
(2009/12/02)
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- IBX-I2 redox couple for facile generation of IOH and I +: Expedient protocol for iodohydroxylation of olefins and iodination of aromatics
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(Chemical Equation Presented) IBX is readily reduced to IBAin the presence of molecular iodine in DMSO to generate hypoiodous acid (IOH), which reacts with a variety of olefins as well as R, β-unsaturated ketones leading to their respective iodohydrins with anti stereochemistry. The same redox chemistry in acetonitrile containing TFA produces iodonium ions for facile iodination of a variety of aromatic compounds in respectable isolated yields.
- Moorthy, Jarugu Narasimha,Senapati, Kalyan,Kumar, Sarvesh
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supporting information; experimental part
p. 6287 - 6290
(2009/12/08)
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- Iodination of activated aromatic compounds using sodium peroxodisulfate and iodine: An efficient way to iodinate alkylated calix[4]arenes
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A simple method for the iodination of activated arenes, using molecular iodine and sodium peroxodisulfate as the oxidant, is presented. The reaction is conducted in the presence of catalytic amounts of tetramethylammonium iodide as a phase-transfer catalyst in acetonitrile. For non-polar substances, which are not soluble in pure acetonitrile such as calix[4]arenes bearing long alkyl chains, a modified reaction is introduced. In this case the phase-transfer catalyst is changed to methyltriphenylphosphonium peroxodisulfate. Chloroform as a cosolvent mediates solubility. Furthermore, we show that the slightly basic conditions obtained upon the addition of sodium bicarbonate have a beneficial effect on the yield. Georg Thieme Verlag Stuttgart.
- Barton, Olaf G.,Mattay, Jochen
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p. 110 - 114
(2008/09/20)
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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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- Palladium-catalyzed silylation of aryl chlorides with hexamethyldisilane
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A method for the palladium-catalyzed silylation of aryl chlorides has been developed. The method affords desired product in good yield, is tolerant of a variety of functional groups, and provides access to a wide variety of aryltrimethylsilanes from commercially available aryl chlorides. Additionally, a one-pot procedure that converts aryl chlorides into aryl iodides has been developed.
- McNeill, Eric,Barder, Timothy E.,Buchwald, Stephen L.
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p. 3785 - 3788
(2008/02/12)
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- Method for separating substances
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An objective of the present invention is to provide electrophoretic separation methods and devices that enable the various features of a substrate surface that comes in contact with an electrophoresis medium to be controlled. The present invention provides methods for electrophoresing substances, which comprises the steps of: (a) adding a substance to be analyzed to an electrophoresis medium retained in a substrate, whose surface that has come in contact with the electrophoresis medium has been coated with a polymer membrane; and (b) adding electrophoretic pressure to the electrophoresis medium. For example, the use of a plasma-polymerized membrane allows the formation of a membrane with homogeneous quality and thickness on the surface of an arbitrary shape. In addition, desired characteristics can be conferred on the surface through selection of monomeric substances. Protein adsorption onto micro-chips can be effectively prevented as well.
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- Efficient copper-catalyzed N-arylation of sulfoximines with aryl iodides and aryl bromides
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Two simple and inexpensive systems for copper-catalyed N-arylations of sulfoximines with aryl bromides and aryl iodides have been developed. Using 10 mol % of a copper(I) salt in combination with 20 mol % of a 1,2-diamine and Cs2CO3 provides N-arylated sulfoximines in high yields. Various functional groups and heteroatoms are tolarated. The method is complementary to the known protocols for N-arylations of sulfoximines, which require stoichiometric quantities of copper salts or cost-intensive palladium/BINAP catalysts.
- Sedelmeier, Joerg,Bolm, Carsten
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p. 6904 - 6906
(2007/10/03)
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- A facile synthesis of aryl iodides via potassium aryltrifluoroborates
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Aryl- and heteroaryltrifluoroborates are rapidly converted to aryl and heteroaryl iodides under mild conditions using sodium iodide in the presence of mild oxidizing agents.
- Kabalka, George W.,Mereddy, Arjun R.
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p. 343 - 345
(2007/10/03)
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- COPPER-CATALYZED FORMATION OF CARBON-HETEROATOM AND CARBON-CARBON BONDS
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One aspect of the present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-sulfur bond between the sulfur atom of a thiol moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper(II)-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-carbon bond between the carbon atom of cyanide ion and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In another embodiment, the present invention relates to a copper-catalyzed method of transforming and aryl, heteroaryl, or vinyl iodide. Yet another embodiment of the present invention relates to a tandem method, which may be practiced in a single reaction vessel, wherein the first step of the method involves the copper-catalyzed formation of an aryl, heteroaryl, or vinyl iodide from the corresponding aryl, heteroaryl, or vinyl chloride or bromide; and the second step of the method involves the copper-catalyzed formation of an aryl, heteroaryl, or vinyl nitrile, amide or sulfide from the aryl, heteroaryl, or vinyl iodide formed in the first step.
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- Directly Observed Reductive Elimination of Aryl Halides from Monomeric Arylpalladium(II) Halide Complexes
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Monomeric, three-coordinate arylpalladium(II) halide complexes undergo reductive elimination of aryl halide to form free haloarene and Pd(0). Reductive elimination of aryl chlorides, bromides, and iodides were observed upon the addition of P(t-Bu)3/
- Roy, Amy H.,Hartwig, John F.
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p. 13944 - 13945
(2007/10/03)
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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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