- Conformational structure and energetics of 2- methylphenyl(2′methoxyphenyl)iodonium chloride: Evidence for solution clusters
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Diaryliodonium salts allow the efficient incorporation of cyclotronproduced [18F]fluoride ions into electron-rich and electron-deficient arenes to provide potential radiotracers for molecular imaging in vivo with positron emission tomography (P
- Lee, Yong-Sok,Hodoscek, Milan,Chun, Joong-Hyun,Pike, Victor W.
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- Cu-catalyzed [2 + 2 + 1] cascade annulation of vinyl iodonium salts with elemental sulfur/selenium for the modular synthesis of thiophenes and selenophenes
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A [2 + 2 + 1] annulation protocol has been established for the modular synthesis of 2,4-disubstituted thiophenes/selenophenes, with excellent regioselectivity. The reactions have been catalyzed by copper salt with elemental sulfur and selenium serving as
- Chen, Chao,Wang, Fei,Wu, Chao,Wu, Yaxing
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p. 945 - 949
(2022/02/01)
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- Applications of hypervalent iodine(III) reagents in constructing ortho-iodo aromatic ethers
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A one-pot method for the synthesis of aromatic ethers using hypervalent iodine(III) reagents obtained from the corresponding iodoaryl compounds is developed. In this concise method, six diaryl ethers and three heterocyclic aromatic ethers are synthesized in good yields. Furthermore, possible mechanisms for the syntheses of the hypervalent iodine reagents and construction of the aromatic ethers are proposed.
- Bao-Hua, Hou,De-Jun, Zhou,Ke-Yang, Wang,Peng-Wei, Liu,Xiao-Rui, Cui,Xue-Yan, Li,Xue-Yun, Gong,Yan-Feng, Sun,Yang-Yang, Zhai,Zhen-Hui, Wang
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p. 818 - 822
(2021/04/22)
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- Preparation and Synthetic Applicability of Imidazole-Containing Cyclic Iodonium Salts
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A novel approach to the preparation of imidazole-substituted cyclic iodonium salts has been developed via the oxidative cyclization of 1-phenyl-5-iodoimidazole using a cheap and available Oxone/H2SO4 oxidative system. The structure of the new polycyclic heteroarenes has been confirmed by single-crystal X-ray diffractometry, revealing the characteristic structure features for cyclic iodonium salts. The newly produced imidazole-flanked cyclic iodonium compounds were found to readily engage in a heterocyclization reaction with elemental sulfur, affording benzo[5,1-b]imidazothiazoles in good yields.
- Antonkin, Nikita S.,Vlasenko, Yulia A.,Yoshimura, Akira,Smirnov, Vladimir I.,Borodina, Tatyana N.,Zhdankin, Viktor V.,Yusubov, Mekhman S.,Shafir, Alexandr,Postnikov, Pavel S.
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p. 7163 - 7178
(2021/05/29)
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- N -Heterocyclic Carbene-Catalyzed Olefination of Aldehydes with Vinyliodonium Salts to Generate α,β-Unsaturated Ketones
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An organocatalyzed metal-free, direct olefination of aldehydes with vinyliodonium salts has been achieved by an N-heterocyclic carbene-promoted C-H bond activation. The reaction proceeds under very mild conditions, delivering a range of (hetero)aryl-vinyl ketones in good yields. The retention of the double bond configuration is uniformly observed, and the application of 2-methoxyphenyl auxiliary group in iodonium salts secures a complete selectivity of the vinyl transfer.
- Rajkiewicz, Adam A.,Kalek, Marcin
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supporting information
p. 1906 - 1909
(2018/04/16)
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- Heterocyclic ring aromatic ether compound and synthesis method thereof
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The invention discloses a heterocyclic ring aromatic ether compound and a synthesis method thereof, and belongs to the technical field of organic synthesis. The heterocyclic ring aromatic ether compound is mainly characterized in that the heterocyclic ring aromatic ether compound has the following structure general formula shown as the accompanying drawing, wherein R1 and R2 are correspondingly and respectively shown as follows: (1) R1 H, and R2 is H; (2) R1 is H, and R2 is Me; (3) R1 is Me, and R2 H. The invention concretely discloses the synthesis method of the heterocyclic ring aromatic ether compound. A mixed solution of acetic anhydride and acetic acid is used for replacing peroxyacetic acid or trifluoromethanesulfonic acid with high corrosiveness; the operation is safer and easier; the industrial production is facilitated; in addition, the heterocyclic ring aromatic ether compound is obtained through oxidizing 4-pyridone by iodonium oxidizing agents.
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Paragraph 0038; 0039; 0040
(2017/07/19)
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- An Investigation of (Diacetoxyiodo)arenes as Precursors for Preparing No-Carrier-Added [18F]Fluoroarenes from Cyclotron-Produced [18F]Fluoride Ion
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Treatment of (diacetoxyiodo)arenes (1a-1u) with cyclotron-produced [18F]fluoride ion rapidly affords no-carrier-added [18F]fluoroarenes (2a-2u) in useful yields and constitutes a new method for converting substituted iodoarenes into substituted [18F]fluoroarenes in just two steps.
- Haskali, Mohammad B.,Telu, Sanjay,Lee, Yong-Sok,Morse, Cheryl L.,Lu, Shuiyu,Pike, Victor W.
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p. 297 - 302
(2016/01/15)
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- Enantioselective Palladium-Catalyzed Alkenylation of Trisubstituted Alkenols to Form Allylic Quaternary Centers
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In this report, we describe the generation of remote allylic quaternary stereocenters β, γ, and δ relative to a carbonyl in high enantioselectivity. We utilize a redox-relay Heck reaction between alkenyl triflates and acyclic trisubstituted alkenols of varying chain-lengths. A wide array of terminal (E)-alkenyl triflates are suitable for this process. The utility of this functionalization is validated further by conversion of the products, via simple organic processes to access remotely functionalized chiral tertiary acid, amine, and alcohol products.
- Patel, Harshkumar H.,Sigman, Matthew S.
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supporting information
p. 14226 - 14229
(2016/11/13)
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- NH-Heterocyclic Aryliodonium Salts and their Selective Conversion into N1-Aryl-5-iodoimidazoles
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The synthesis of N-arylimidazoles substituted at the sterically encumbered 5-position is a challenge for modern synthetic approaches. A new family of imidazolyl aryliodonium salts is reported, which serve as a stepping stone on the way to selective formation of N1-aryl-5-iodoimidazoles. Iodine acts as a “universal” placeholder poised for replacement by aryl substituents. These new λ3-iodanes are produced by treating the NH-imidazole with ArI(OAc)2, and are converted to N1-aryl-5-iodoimidazoles by a selective copper-catalyzed aryl migration. The method tolerates a variety of aryl fragments and is also applicable to substituted imidazoles.
- Wu, Yichen,Izquierdo, Susana,Vidossich, Pietro,Lledós, Agustí,Shafir, Alexandr
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supporting information
p. 7152 - 7156
(2016/07/06)
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- Copper-Catalyzed Oxy-Alkenylation of Homoallylic Alcohols to Generate Functional syn-1,3-Diol Derivatives
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A novel method for the synthesis of a wide range of functionalized 1,3-diol derivatives is reported. Employing a copper-catalyzed oxy-alkenylation strategy, a range of readily available, substituted homoallylic alcohol derivatives and alkenyl(aryl) iodonium salts combine to form syn-1,3-carbonates in excellent yield and with high selectivity. Furthermore, the products formed are amenable to an iterative reaction sequence, thus affording highly complex polyketide-like fragments. Polyols: The reported copper-catalyzed oxy-alkenylation strategy works well for a range of readily available, substituted homoallylic alcohol derivatives and alkenyl(aryl) iodonium salts to form syn-1,3-carbonates in excellent yield and high selectivity. Furthermore, the products formed are amenable to an iterative reaction sequence, thus affording highly complex polyketide-like fragments.
- Holt, Dean,Gaunt, Matthew J.
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supporting information
p. 7857 - 7861
(2015/06/30)
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- Synthesis of ionic-liquid-supported diaryliodonium salts
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The synthesis of ionic-liquid-supported diaryliodonium salts is described. The synthesis is simple and practical, and the ionic liquid products require no chromatographic purification. The ionic-liquid-supported diaryliodonium salts are quite stable, and they did not show any sign of decomposition or loss of reactivity, even after being stored for one month at 5 °C. The reactivity of these salts was explored in the phenylation of substituted phenols and carboxylic acids, and the corresponding diaryl ethers and aryl esters, respectively, were synthesized in good to excellent yields and with high purities.
- Kumar Muthyala, Manoj,Choudhary, Sunita,Pandey, Khima,Shelke, Ganesh M.,Jha, Mukund,Kumar, Anil
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supporting information
p. 2365 - 2370
(2014/04/17)
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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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- Fast and high-yield microreactor syntheses of ortho -substituted [ 18F]Fluoroarenes from reactions of [18F]Fluoride ion with diaryliodonium salts
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A microreactor was applied to produce ortho-substituted [ 18F]fluoroarenes from the reactions of cyclotron-produced [ 18F]fluoride ion (t1/2 = 109.7 min) with diaryliodonium salts. The microreactor provided a very convenient means for running sequential reactions rapidly with small amounts of reagents under well-controlled conditions, thereby allowing reaction kinetics to be followed and Arrhenius activation energies (Ea) to be measured. Prepared symmetrical iodonium chlorides (Ar2I+Cl-) rapidly (6H4, 51%) to high (Ar = Ph or 2-MeC6H4, 85%) decay-corrected radiochemical yields (RCYs) of a single radioactive product (Ar18F). Reaction velocity with respect to Ar group was 2-MeOC6H4 6H4. Activation energies were in the range 18-28 kcal/mol. Prepared unsymmetrical salts (e.g., 2-RC6H 4I+2′-R′C6H4X -; X = Cl or OTs) also rapidly gave two products (2-RC 6H418F and 2-R′C6H 418F) in generally high total RCYs (79-93%). Selectivity for product [18F]fluoroarene was controlled by the nature of the ortho substituents. The power of ortho substituents to impart an ortho-effect was in the following order:, 2,6-di-Me > 2,4,6-tri-Me > Br > Me > Et ≈ iPr ? H > OMe. For (2-methyphenyl)(phenyl)iodonium chloride, the time-course of reaction product selectivity was constant and consistent with the operation of the Curtin-Hammett principle. These results will aid in the design of diaryliodonium salt precursors to 18F- labeled tracers for molecular imaging. This article not subject to U.S. Copyright. Published 2010 by the American Chemical Society.
- Chun, Joong-Hyun,Lu, Shuiyu,Lee, Yong-Sok,Pike, Victor W.
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supporting information; experimental part
p. 3332 - 3338
(2010/08/20)
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- Easy and safe preparations of (diacetoxyiodo)arenes from iodoarenes, with Urea-Hydrogen Peroxide adduct (UHP) as the oxidant and the fully interpreted 1H- and 13C-NMR spectra of the products
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An easy and safe, though only moderately effective method is presented for preparing (diacetoxyiodo)arenes, ArI(OAc)2, from iodoarenes, ArI, using the commercially available and easily handled urea-hydrogen peroxide adduct (UHP) as the oxidant. The reactions take place in anhydrous AcOH/Ac2O/AcONa (a catalyst) mixtures, at 40°C for 3.5 h to afford the purified ArI(OAc)2 in 37-78% yields. The fully interpreted 1H- and 13C-NMR spectra of the ArI(OAc)2 products are reported.
- Zielinska, Agnieszka,Skulski, Lech
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p. 190 - 194
(2007/10/03)
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- Easy preparation of (diacetoxyiodo)arenes from iodoarenes with sodium percarbonate as the oxidant
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Easy and effective preparations of nearly pure (diacetoxyiodo)arenes, ArI(OAc)2, from iodoarenes, ArI, are reported. In most cases the crude colorless products thus obtained need not be further purified, i.e., by recrystallization. As an example, the PhI(OAc)2 thus prepared was 99% pure (by iodometry).
- Zielinska, Agnieszka,Skulski, Lech
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p. 806 - 809
(2007/10/03)
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- Syntheses of (diacetoxyiodo)arenes or iodylarenes from iodoarenes, with sodium periodate as the oxidant
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Easy, safe, and effective novel methods for preparing either (diacetoxyiodo)-(arenes, ArI(OAc)2, or iodylarenes, ArIO2, from the corresponding iodoarenes, ArI, using sodium periodate as the oxidant are presented in this paper. In order to obtain 2- and 4-iodylbenzoic acids, the respective sodium salts of 2- and 4-iodobenzoic acids should be used as the starting substrates, because mixtures containing the corresponding iodosyl derivatives as the main products along with the intended iodyl compounds are produced from the free parent acids.
- Kazmierczak, Pawel,Skulski, Lech,Kraszkiewicz, Lukasz
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p. 881 - 891
(2007/10/03)
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- Synthesis of functionalised unsymmetrical diaryliodonium salts
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A generalised synthesis of unsymmetrical functionalised diaryliodonium salts has been developed through the direct reaction of bis(acetoxy)iodoarenes with arenes in a trifluoromethanesulfonic or trifluoroacetic acid medium.
- Shah, Aneela,Pike, Victor W.,Widdowson, David A.
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p. 2463 - 2465
(2007/10/03)
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- FURTHER FUNCTIONAL GROUP OXIDATIONS USING SODIUM PERBORATE
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Sodium perborate in acetic acid is an effective reagent for the oxidation of aromatic aldehydes to carboxylic acids, iodoarenes to (diacetoxyiodo)arenes, azines to N-oxides, and various types of sulfur heterocycles to S,S-dioxides.Nitriles are unaffected by the reagent in acetic acid, but undergo smooth hydration to amides when aqueous methanol is employed as solvent.
- McKillop, Alexander,Kemp, Duncan
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p. 3299 - 3306
(2007/10/02)
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- Regiospecific Synthesis of Aryl(2-furyl)iodonium Tosylates, a New Class of Iodonium Salts, from arenes and 2-(Trimethylsilyl)furans in Organic Solvents
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The treatment of 2,5-bis(trimethylsilyl)furan with various arenes (ArI(OH)OTs) in acetonitrile/ methanol has been found to give aryliodonium tosylates in yields ranging from 62percent to 80percent.With 2-methyl-5-(trimethylsilyl)furan as the substrate, aryl(5-methyl-2-furyl)iodonium tosylates are likewise obtained in yields ranging from 61percent to 74percent.The reactions of arenes with 2-(trimethylsilyl)furan in methanol give aryl(2-furyl)iodonium tosylates in much lower yield (9-23percent) and are accompanied by the reductive decomposition of the hypervalent organoiodine component.To our knowledge, these are the first reported examples of aryl(furyl)iodonium salts.
- Carman, Carol S.,Koser, Gerald F.
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p. 2534 - 2539
(2007/10/02)
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