- Copper-catalyzed arylation of polycyclic aromatic hydrocarbons by the PO group
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The first example of a directed and regioselective arylation of polycyclic aromatic hydrocarbons (PAHs) by using a PO directing group is reported herein. The protocol uses a cheap copper catalyst, and results in a breakthrough meta-selective C-H functionalization of arylphosphine oxide compounds. Substrates with potential fluorescence properties, for example, pyrene and fluoranthene, were successfully arylated under the system, thus achieving an efficient modification of fluorescent molecules containing the PO functional group. This journal is
- Niu, Yuan,Qi, Zhichao,Lou, Qinxin,Bai, Pengbo,Yang, Shangdong
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- Palladium Catalyzed Regioselective Cyclization of Arylcarboxylic Acids via Radical Intermediates with Diaryliodonium Salts
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Palladium-catalyzed C2-arylation/intramolecular acylation with arylcarboxylic acids was developed by using diaryliodonium salts. The protocol has the advantage of good step-economy by two chemical bonds formation in one pot.
- An, Guoqiang,Wang, Limin,Han, Jianwei
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supporting information
p. 8688 - 8693
(2021/11/24)
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- Synthesis of Diverse Aryliodine(III) Reagents by Anodic Oxidation?
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An anodic oxidation enabled synthesis of hypervalent iodine(III) reagents from aryl iodides is demonstrated. Under mild electrochemical conditions, a range of aryliodine(III) reagents including iodosylarenes, (difunctionaliodo)arenes, benziodoxoles and diaryliodonium salts can be efficiently synthesized and derivatized in good to excellent yields with high selectivity. As only electrons serve as the oxidation reagents, this method offers a more straightforward and sustainable manner avoiding the use of expensive or hazardous chemical oxidants.
- Zu, Bing,Ke, Jie,Guo, Yonghong,He, Chuan
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supporting information
p. 627 - 632
(2021/02/12)
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- N1- and N3-Arylations of Hydantoins Employing Diaryliodonium Salts via Copper(I) Catalysis at Room Temperature
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Copper(I)-catalyzed N-arylation (both N1- and N3-) of hydantoins with diaryliodonium salts as aryl partners at room temperature is reported. The transformation allows diverse scopes on both hydantoins and diaryliodonium salts deliver
- Abha Saikia, Raktim,Barman, Dhiraj,Dutta, Anurag,Jyoti Thakur, Ashim
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supporting information
p. 400 - 410
(2020/12/17)
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- Versatile and base-free copper-catalyzed α-arylations of aromatic ketones using diaryliodonium salts
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A ligand and base-free copper catalyzed synthetic method for the efficient α-arylation of aromatic ketones is described. In order to avoid strong bases, ketone-derived silyl enol ethers were employed. Their reaction with diaryliodonium salts as aryl source provided the intermolecular C–C coupling displaying good functional group tolerance and requiring low catalyst loading.
- Bouquin, Maxime,Jaroschik, Florian,Taillefer, Marc
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supporting information
(2021/06/11)
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- Direct Copper-Catalyzed C-3 Arylation of Diphenylphosphine Oxide Indoles
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We have developed a simple and effective method for the C-3 arylation of phosphorus-containing indole compounds in the presence of CuI under mild conditions. This reaction provides a reliable method for the modification of ligands.
- Huang, Xiao-Ling,Li, Chong,Wang, Juan,Yang, Shang-Dong
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supporting information
(2021/10/25)
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- Direct C-H α-Arylation of Enones with ArI(O2CR)2 Reagents
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α-Arylation of α,β-unsaturated ketones constitutes a powerful synthetic transformation. It is most commonly achieved via cross-coupling of α-haloenones, but this stepwise strategy requires prefunctionalized substrates and expensive catalysts. Direct enone C-H α-arylation would offer an atom- and step-economical alternative, but such reports are scarce. Herein we report the metal-free direct C-H arylation of enones mediated by hypervalent iodine reagents. The reaction proceeds via a reductive iodonium Claisen rearrangement of in situ-generated β-pyridinium silyl enol ethers. The aryl groups are derived from ArI(O2CCF3)2 reagents, which are readily accessed from the parent iodoarenes. The reaction is tolerant of a wide range of substitution patterns, and the incorporated arenes maintain the valuable iodine functional handle. Mechanistic investigations implicate arylation via an umpoled "enolonium" species and show that the presence of a β-pyridinium moiety is critical for the desired C-C bond formation.
- Sousa E Silva, Felipe Cesar,Van, Nguyen T.,Wengryniuk, Sarah E.
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supporting information
p. 64 - 69
(2020/01/22)
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- Lewis Acidity Scale of Diaryliodonium Ions toward Oxygen, Nitrogen, and Halogen Lewis Bases
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Equilibrium constants for the associations of 17 diaryliodonium salts Ar2I+X- with 11 different Lewis bases (halide ions, carboxylates, p-nitrophenolate, amines, and tris(p-anisyl)phosphine) have been investigated by titrations followed by photometric or conductometric methods as well as by isothermal titration calorimetry (ITC) in acetonitrile at 20 °C. The resulting set of equilibrium constants KI covers 6 orders of magnitude and can be expressed by the linear free-energy relationship lg KI = sI LAI + LBI, which characterizes iodonium ions by the Lewis acidity parameter LAI, as well as the iodonium-specific affinities of Lewis bases by the Lewis basicity parameter LBI and the susceptibility sI. Least squares minimization with the definition LAI = 0 for Ph2I+ and sI = 1.00 for the benzoate ion provides Lewis acidities LAI for 17 iodonium ions and Lewis basicities LBI and sI for 10 Lewis bases. The lack of a general correlation between the Lewis basicities LBI (with respect to Ar2I+) and LB (with respect to Ar2CH+) indicates that different factors control the thermodynamics of Lewis adduct formation for iodonium ions and carbenium ions. Analysis of temperature-dependent equilibrium measurements as well as ITC experiments reveal a large entropic contribution to the observed Gibbs reaction energies for the Lewis adduct formations from iodonium ions and Lewis bases originating from solvation effects. The kinetics of the benzoate transfer from the bis(4-dimethylamino)-substituted benzhydryl benzoate Ar2CH-OBz to the phenyl(perfluorophenyl)iodonium ion was found to follow a first-order rate law. The first-order rate constant kobs was not affected by the concentration of Ph(C6F5)I+ indicating that the benzoate release from Ar2CH-OBz proceeds via an unassisted SN1-type mechanism followed by interception of the released benzoate ions by Ph(C6F5)I+ ions.
- Legault, Claude Y.,Mayer, Robert J.,Mayr, Herbert,Ofial, Armin R.
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supporting information
(2020/03/13)
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- Benzanthrone derivative and preparation method thereof and application thereof in functional pigments
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The invention discloses a benzanthrone derivative and a preparation method thereof. The general formula is shown as a formula I or IV, formula I or IV, R1, R2, R3 is independently selected from hydrogen, halogen, an ester group, an acyl group, a branched-chain or straight-chain C1-C20 alkyl group, a straight-chain or branched-chain C1-C20 alkoxy group, a branched-chain or straight-chain perfluoroC1-C20 alkyl group, a branched-chain or straight-chain perfluoroC1-C20 alkoxy group, a substituted or unsubstituted C4-C40 aryl group, and a substituted or unsubstituted C4-C40 heteroaryl group. The benzanthrone derivative with a novel structure provided by the invention is simple in preparation method, non-toxic and harmless, has yellow fluorescence, can be used as a potential organic functional material, and is an important dye intermediate.
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Paragraph 0040-0041
(2020/07/24)
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- Synthesis of phenols and aryl silyl ethers via arylation of complementary hydroxide surrogates
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Two transition-metal-free methods to access substituted phenols via the arylation of silanols or hydrogen peroxide with diaryliodonium salts are presented. The complementary reactivity of the two nucleophiles allows synthesis of a broad range of phenols without competing aryne formation, as illustrated by the synthesis of the anesthetic Propofol. Furthermore, silyl-protected phenols can easily be obtained, which are suitable for further transformations.
- Reitti, Marcus,Gurubrahamam, Ramani,Walther, Melanie,Lindstedt, Erik,Olofsson, Berit
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supporting information
p. 1785 - 1788
(2018/04/14)
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- Visible Light Accelerated Vinyl C–H Arylation in Pd-Catalysis: Application in the Synthesis of ortho Tetra-substituted Vinylarene Atropisomers
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A visible light accelerated C–H functionalization reaction in palladium-catalyzed arylation of vinyl arenes with diaryliodonium salts is reported in the absence of additional photosensitizer. The kinetic isotope effect (kH/kD) was ch
- Feng, Jia,Li, Bin,Jiang, Julong,Zhang, Mingkai,Ouyang, Wenbai,Li, Chunyu,Fu, Yao,Gu, Zhenhua
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supporting information
p. 11 - 14
(2017/11/23)
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- Preparation method of trifluoromethanesulfonic acid diaryl iodonium salt and derivative thereof
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The invention relates to a preparation method of a trifluoromethanesulfonic acid diaryl iodonium salt and a derivative thereof. The method includes: adding m-chloroperoxybenzoic acid, an iodobenzene compound, a dichloromethane solution, a benzene compound
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Paragraph 0019; 0020; 0021; 0022; 0023; 0024; 0025; 0026
(2018/03/24)
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- Transition metal-free, chemoselective arylation of thioamides yielding aryl thioimidates or N-aryl thioamides
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Reactions of secondary thioamides with diaryliodonium salts under basic, transition metal-free conditions resulted in chemoselective S-arylation to provide aryl thioimidates in good to excellent yields. Equimolar amounts of thioamide, base and diaryliodonium salt were sufficient to obtain a diverse selection of products within short reaction times. Reactions with thiolactams delivered N-arylated thioamides in good yield at room temperature.
- Villo, Piret,Kervefors, Gabriella,Olofsson, Berit
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supporting information
p. 8810 - 8813
(2018/08/17)
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- Regiospecific N-Arylation of Aliphatic Amines under Mild and Metal-Free Reaction Conditions
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A transition metal-free N-arylation of primary and secondary amines with diaryliodonium salts is presented. Both acyclic and cyclic amines are well tolerated, providing a large set of N-alkyl anilines. The methodology is unprecedented among metal-free methods in terms of amine scope, the ability to transfer both electron-withdrawing and electron-donating aryl groups, and efficient use of resources, as excess substrate or reagents are not required.
- Purkait, Nibadita,Kervefors, Gabriella,Linde, Erika,Olofsson, Berit
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supporting information
p. 11427 - 11431
(2018/08/28)
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- Flow Synthesis of Diaryliodonium Triflates
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A safe and scalable synthesis of diaryliodonium triflates was achieved using a practical continuous-flow design. A wide array of electron-rich to electron-deficient arenes could readily be transformed to their respective diaryliodonium salts on a gram scale, with residence times varying from 2 to 60 s (44 examples).
- Laudadio, Gabriele,Gemoets, Hannes P. L.,Hessel, Volker,No?l, Timothy
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p. 11735 - 11741
(2017/11/24)
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- A Modular Flow Design for the meta-Selective C?H Arylation of Anilines
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Described herein is an effective and practical modular flow design for the meta-selective C?H arylation of anilines. The design consists of four continuous-flow modules (i.e., diaryliodonium salt synthesis, meta-selective C?H arylation, inline copper extraction, and aniline deprotection) which can be operated either individually or consecutively to provide direct access to meta-arylated anilines. With a total residence time of 1 hour, the desired product could be obtained in high yield and excellent purity without the need for column chromatography, and the residual copper content meets the standards for parenterally administered pharmaceutical substances.
- Gemoets, Hannes P. L.,Laudadio, Gabriele,Verstraete, Kirsten,Hessel, Volker,No?l, Timothy
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supporting information
p. 7161 - 7165
(2017/06/13)
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- Efficient O-Functionalization of Carbohydrates with Electrophilic Reagents
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Novel methodology for O-functionalization of carbohydrate derivatives has been established using bench-stable and easily prepared iodonium(III) reagents. Both electron-withdrawing and electron-donating aryl groups were introduced under ambient conditions and without precautions to exclude air or moisture. Furthermore, the approach was extended both to full arylation of cyclodextrin, and to trifluoroethylation of carbohydrate derivatives. This is the first general approach to introduce traditionally non-electrophilic groups into any of the OH groups around the sugar backbone. The methodology will be useful both in synthetic organic chemistry and biochemistry, as important functional groups can be incorporated under simple and robust reaction conditions in a fast and efficient manner.
- Tolnai, Gergely L.,Nilsson, Ulf J.,Olofsson, Berit
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supporting information
p. 11226 - 11230
(2016/10/13)
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- One-Pot C?H Functionalization of Arenes by Diaryliodonium Salts
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A transition-metal-free, mild, and highly regioselective synthesis of nitroarenes from arenes has been developed. The products are obtained in a sequential one-pot reaction by nitration of iodine(III) reagents with two carbon ligands, which are formed in situ from iodine(I). This novel concept has been extended to formation of aryl azides, and constitutes an important step towards catalytic reactions with these hypervalent iodine reagents. An efficient nitration of isolated diaryliodonium salts has also been developed, and the mechanism is proposed to proceed by a [2,2] ligand coupling pathway.
- Reitti, Marcus,Villo, Piret,Olofsson, Berit
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supporting information
p. 8928 - 8932
(2016/07/26)
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- Palladium(II) oxide impregnated on magnetite as a catalyst for the synthesis of 4-arylcoumarins: Via a Heck-arylation/cyclization process
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Heck-arylation/cyclization was achieved using heterogeneous palladium(ii) oxide impregnated on magnetite catalyst (2.5 mol%) with a lower catalyst loading than that reported for similar processes. Ethanol was used as a non-toxic and bio-renewable solvent. Good yields were afforded using a broad range of substrates (40-98%). The catalyst could be partially recycled, and analyses confirmed the almost total reduction of palladium(ii) oxide to palladium(0) as well as the iodine poissoning effect, which is the main barrier to complete recyclability.
- Pérez, Juana M.,Cano, Rafael,McGlacken, Gerard P.,Ramón, Diego J.
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p. 36932 - 36941
(2016/05/24)
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- Access to Indole Derivatives from Diaryliodonium Salts and 2-Alkynylanilines
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An efficient, environmentally friendly, and operationally simple procedure to 1,2-disubstituted indoles from 2-alkynylanilines and diaryliodonium salts has been developed. This reaction proceeds smoothly under metal-free conditions. The products obtained could be transferred into 3,3′-diindolylmethane with DMSO catalyzed by palladium. The isotopic label experiments indicated that the methylene group in 3,3′-diindolylmethane is derived from DMSO. The diverse indoles were obtained in up to 90% yield for 28 examples.
- Li, Pengfei,Weng, Yunxiang,Xu, Xianxiang,Cui, Xiuling
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p. 3994 - 4001
(2016/06/09)
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- Well-Defined, Shelf-Stable (NHC)Ag(CF2H) Complexes for Difluoromethylation
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The preparation of the thermally stable, well-defined NHC-ligated difluoromethylated silver complexes 1a,b is described. The complexes were fully characterized, and the structural assignments were ambiguously further confirmed by single-crystal X-ray diffraction. Reactions of [(SIPr)Ag(CF2H)] with a variety of activated electrophiles such as diaryliodonium salts, vinyl(aryl)iodonium salts, aryldiazonium salts, and acid chlorides in the presence or absence of CuI occurred smoothly at room temperature to generate difluoromethylated compounds in good to excellent yields. (Chemical Equation Presented).
- Gu, Yang,Chang, Dalu,Leng, Xuebing,Gu, Yucheng,Shen, Qilong
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supporting information
p. 3065 - 3071
(2015/06/30)
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- Metal-Free C-Arylation of Nitro Compounds with Diaryliodonium Salts
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An efficient, mild, and metal-free arylation of nitroalkanes with diaryliodonium salts has been developed, giving easy access to tertiary nitro compounds. The reaction proceeds in high yields without the need for excess reagents and can be extended to α-arylation of nitroesters. Nitroalkanes were selectively C-arylated in the presence of other easily arylated functional groups, such as phenols and aliphatic alcohols.
- Dey, Chandan,Lindstedt, Erik,Olofsson, Berit
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supporting information
p. 4554 - 4557
(2015/09/28)
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- Transition metal-free direct C-H functionalization of quinones and naphthoquinones with diaryliodonium salts: Synthesis of aryl naphthoquinones as β-secretase inhibitors
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A novel ligand-free, transition metal-free direct C.H functionalization of quinones with diaryliodonium salts has been developed for the first time. The transformation was promoted only through the use of a base and gave aryl quinone derivatives in moderate to good yields. This methodology provided an effective and easy way to synthesize β-secretase inhibitors. The radical trapping experiments showed that this progress was the radical mechanism.
- Wang, Dawei,Ge, Bingyang,Li, Liang,Shan, Jie,Ding, Yuqiang
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supporting information
p. 8607 - 8613
(2015/01/08)
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- Arylation with unsymmetrical diaryliodonium salts: A chemoselectivity study
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Phenols, anilines, and malonates have been arylated under metal-free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new "anti-ortho effect" has been identified in the arylation of malonates. Several "dummy groups" have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal-free reagents. Copyright
- Malmgren, Joel,Santoro, Stefano,Jalalian, Nazli,Himo, Fahmi,Olofsson, Berit
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p. 10334 - 10342
(2013/09/02)
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- Copper(II)-catalyzed meta-selective direct arylation of α-aryl carbonyl compounds
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Strong competition: A method for the meta-selective arylation of the highly versatile α-aryl carbonyl motif using diaryliodonium salts is described. In this CuII-catalyzed process the remote carbonyl group is capable of overpowering even strongly para-directing functionalities to form the elusive meta-products (see scheme). Remarkably, the arylation process can also operate under metal-free conditions.
- Duong, Hung A.,Gilligan, Ruth E.,Cooke, Michael L.,Phipps, Robert J.,Gaunt, Matthew J.
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supporting information; experimental part
p. 463 - 466
(2011/03/16)
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- Tandem indole C-H alkenylation/arylation for tetra-substituted alkene synthesis
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Alkynyl indoles undergo a novel sequence of Pd-catalysed indole C-H activation/alkyne carbopalladation/arylation, with diaryliodonium salts providing the aryl components. An array of functionalised indole alkenes have been prepared in good to excellent yield, with the reaction being selective for the Z-alkene.
- Suarez, Laura Lopez,Greaney, Michael F.
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supporting information; experimental part
p. 7992 - 7994
(2011/08/07)
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- Synthesis of diaryliodonium triflates using environmentally benign oxidizing agents
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A range of symmetric and unsymmetric diaryliodonium triflates have been prepared employing urea-hydrogen peroxide as the oxidizing agent. The use of aqueous hydrogen peroxide and catalytic systems with methylrhenium trioxide in the oxidation of iodoarenes
- Merritt, Eleanor A.,Malmgren, Joel,Klinke, Felix J.,Olofsson, Berit
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experimental part
p. 2277 - 2280
(2009/12/08)
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- High-yielding one-pot synthesis of diaryliodonium triflates from arenes and iodine or aryl iodides
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Unsymmetric and symmetric diaryliodonium triflates are synthesized from both electron-deficient and electron-rich substrates in a fast, high yielding, and operationally simple protocol employing arenes and aryl iodides or iodine. The Royal Society of Chem
- Bielawski, Marcin,Olofsson, Berit
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p. 2521 - 2523
(2008/02/11)
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- Efficient and general one-pot synthesis of diaryliodonium triflates: Optimization, scope and limitations
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Symmetrical and unsymmetrical diaryliodonium triflates have been synthesized from both electron-deficient and electron-rich arenes and aryl iodides with mCPBA and triflic acid. A thorough investigation of the optimization, scope and limitations has resulted in an improved one-pot protocol that is fast, high-yielding, and operationally simple. The reaction has been extended to the direct synthesis of symmetrical iodonium salts from iodine and arenes, conveniently circumventing the need for aryl iodides.
- Bielawski, Marcin,Zhu, Mingzhao,Olofsson, Berit
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p. 2610 - 2618
(2008/09/19)
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- Novel anthracene derivative and radiation-sensitive resin composition
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A novel anthracene derivative useful as an additive to a radiation-sensitive resin composition is disclosed. The anthracene derivative has the following formula (1), wherein R1 groups individually represent a hydroxyl group or a monovalent organic group having 1-20 carbon atoms, n is an integer of 0-9, X is a single bond or a divalent organic group having 1-12 carbon atoms, and R2 represents a monovalent acid-dissociable group. The radiation-sensitive resin composition comprises the anthracene derivative of the formula (1), a resin insoluble or scarcely soluble in alkali, but becomes alkali soluble in the presence of an acid, and a photoacid generator. The composition is useful as a chemically-amplified resist for microfabrication utilizing deep ultraviolet rays, typified by a KrF excimer laser and ArF excimer laser.
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- The first aryne evolution from the reactions of selenonium salts with aryllithiums
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The first example of the benzyne generation was found in the reactions of alkynylselenonium salt 1a with 1.0 equiv. of phenyllithium in THF at room temperature for 3 h. The formation of the aryne intermediate was confirmed in the reactions of alkynylselenonium salt 1b and tri-p-tolylselenonium salt 6b with tolyllithium, which gave a mixture of alkynylbiphenyl derivatives 18 and 19 in 19% yield (18:19=11:8) and a mixture of bitolyls 28 and 29 in 63% yield (28:29=2:1), respectively. The reaction mechanisms of these reactions are discussed. (C) 2000 Elsevier Science Ltd.
- Watanabe, Shin-Ichi,Yamamoto, Keiichirou,Itagaki, Yukiko,Iwamura, Tatsunori,Iwama, Tetsuo,Kataoka, Tadashi
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p. 855 - 863
(2007/10/03)
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- An efficient ligand exchange reaction of (e)-[β- (trifluoromethanesulfonyloxy)ethenyl](phenyl)iodonium triflates with aryl- and alkynyllithium reagents leading to diaryl- and alkynyliodonium triflates
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Reaction of (E)-[β-(trifluoromethanesulfonyloxy)- ethenyl](phenyl)iodonium triflates with aryl- and alkynyllithium reagents gave aryl(phenyl)- and alkynyl(phenyl)iodonium triflates in high yields and selectively. These reactions indicate that ligand exchange takes place efficiently at the hypervalent iodine atom and provides another approach to diaryl- and alkynyliodonium salts.
- Pirguliyev, Namig Sh,Brel, Valery K.,Akhmedov, Navruz G.,Zefirov, Nikolai S.
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- Diaryliodonium fluoroalkyl sulfonate salts and a method of making
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The present invention provides a convenient, simple, safe and efficient one-pot method for the synthesis of a number of diarlyiodonium triflate salts which does not involve sulfuric acid and which eliminates the need for any counter-ion exchange processes. The invention also provides a novel salt of the formula STR1
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- IODOSYL TRIFLUOROMETHANESULFONATE - AN EFFICIENT REAGENT FOR THE SINGLE STEP PREPARATION OF DIARYL IODONIUM TRIFLATE SALTS
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Iodosyl triflate O=I-OTf reacts with the trimethylsilyl derivatives of aromatic compounds under mild conditions forming the corresponding iodonium salts in good yield.
- Stang, Peter J.,Zhdankin, Viktor V.,Tykwinski, Rik,Zefirov, Nikolai S.
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p. 7497 - 7498
(2007/10/02)
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