- Application of [hydroxy(tosyloxy)iodo]benzene in the wittig-ring expansion sequence for the synthesis of β-benzocycloalkenones from α-benzocycloalkenones
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The conversion of α-benzocycloalkenones to homologous β-benzocycloalkenones containing six, seven and eight-membered rings is reported. This was accomplished via a Wittig olefination-oxidative rearrangement sequence using [hydroxy(tosyloxy)iodo]-benzene (HTIB) is the oxidant, that enables the synthesis of regioisomeric pairs of methyl-substituted β-benzocycloalkenones. The incorporation of carbon-13 at C-1 of the β-tetralone nucleus was also demonstrated. The Wittig-HTIB approach is a useful alternative to analogous sequences in which Tl(NO3) 3·3H2O or the Prevost combination (AgNO 3/I2) are employed in the oxidation step.
- Justik, Michael W.,Koser, Gerald F.
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Read Online
- Use of hypervalent iodine reagents in visible light-promoted α-ketoacylations of sulfoximines with aryl alkynes
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In visible light, sulfoximidoyl-containing hypervalent iodine reagents react with aryl alkynes to give N-α-ketoacylated sulfoximines in good to high yields. The process is metal- and base-free, providing the diketonic products without the use of highly ox
- Wang, Chenyang,Ma, Ding,Tu, Yongliang,Bolm, Carsten
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Read Online
- 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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- Continuous-Flow Electrochemical Generator of Hypervalent Iodine Reagents: Synthetic Applications
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An efficient and reliable electrochemical generator of hypervalent iodine reagents has been developed. In the anodic oxidation of iodoarenes to hypervalent iodine reagents under flow conditions, the use of electricity replaces hazardous and costly chemical oxidants. Unstable hypervalent iodine reagents can be prepared easily and coupled with different substrates to achieve oxidative transformations in high yields. The unstable, electrochemically generated reagents can also easily be transformed into classic bench-stable hypervalent iodine reagents through ligand exchange. The combination of electrochemical and flow-chemistry advantages largely improves the ecological footprint of the overall process compared to conventional approaches.
- Elsherbini, Mohamed,Winterson, Bethan,Alharbi, Haifa,Folgueiras-Amador, Ana A.,Génot, Célina,Wirth, Thomas
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supporting information
p. 9811 - 9815
(2019/06/24)
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- SYNTHESIS OF HYPERVALENT IODINE REAGENTS WITH DIOXYGEN
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Methods of synthesis of hypervalent iodine reagents and methods for oxidation of organic compounds are disclosed.
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Paragraph 0085-0086
(2019/01/15)
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- A trivalent hypervalent iodine compound using hypochlorite (by machine translation)
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[A] used in the prior art organic salt, toxic chlorine gas, organic peroxides can be used without the novel trivalent hypervalent iodine compound production. Furthermore, the acyloxy groups other than the trivalent hypervalent iodine compounds having a ligand manufacturing method. (1) Formula [solution](In the formula, R1 Substituted/unsubstituted aromatic group, aliphatic group or the like. N is an integer of 1 or more. ) Represented by the iodine compound, carboxylic acid, carboxylic acid anhydride, a sulfonic acid or sulfonic acid anhydride with at least one organic acid selected from the group consisting of, a hypochlorite mixing, trivalent hypervalent iodine compound. [Drawing] no (by machine translation)
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Paragraph 0064
(2020/02/14)
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- Safer Synthesis of (Diacetoxyiodo)arenes Using Sodium Hypochlorite Pentahydrate
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A practical method for the preparation of (diacetoxyiodo)arene ArI(OAc)2 is described. The use of commercially available sodium hypochlorite pentahydrate (NaClO·5H2O) enabled safe, rapid, and inexpensive oxidation of iodoarenes with electron-withdrawing and -donating substituents. The method allows tandem divergent access to synthetically useful organo-λ3-iodanes such as hydroxyl(tosyloxy)iodobenzene, iodosylbenzene, iodonium ylide, etc.
- Watanabe, Ayumi,Miyamoto, Kazunori,Okada, Tomohide,Asawa, Tomotake,Uchiyama, Masanobu
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p. 14262 - 14268
(2018/11/23)
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- Oxidase catalysis via aerobically generated hypervalent iodine intermediates
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The development of sustainable oxidation chemistry demands strategies to harness O'2 as a terminal oxidant. Oxidase catalysis, in which O'2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O'2 reduction. Direct O'2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O'2 and the disparate electron inventories of four-electron O'2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents - a broadly useful class of selective two-electron oxidants - from O'2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O'2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.
- Maity, Asim,Hyun, Sung-Min,Powers, David C.
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p. 200 - 204
(2018/02/06)
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- α-Sulfonyloxylation of 1,3-dicarbonyl compounds utilizing hypervalent iodine(iii) reagent: Construction of quaternary carbon center
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An efficient method for direct α-sulfonyloxylation of various sterically hindered 1,3-dicarbonyl compounds has been developed under mild reaction conditions. The yields of desired products is up to 90% and a plausible mechanism was accordingly proposed.
- Liu, Ruojuan,Wang, Junzheng,Hu, Wen,Zhang, Xiaohui,Xiong, Yan
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supporting information
p. 1957 - 1965
(2018/07/15)
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- Expeditious trifluoromethylthiolation and trifluoromethylselenolation of alkynyl(phenyl)iodoniums by [XCF3]? (X = S, Se) anions
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Trifluoromethylthiolation and trifluoromethylselenolation of alkynyl(phenyl)iodonium tosylates by [XCF3]? (X = S, Se) ions was accomplished in 5-10 minutes at room temperature under a N2 atmosphere and provided a variety of alkynyl trifluoromethyl sulfides and selenides in good yields. Compared to the known methods, this approach has several advantages such as short reaction times and metal- and additive-free conditions without needing excess [Me4N][XCF3] reagents. Moreover, the less efficient reactions of (phenylethynyl)benziodoxol(on)e with [Me4N][XCF3] under the standard conditions demonstrate that acyclic alkynyl(phenyl)iodoniums are more powerful alkynyl sources in the conversion. This protocol allows for a fast and convenient access to numerous alkynyl trifluoromethyl sulfides and selenides.
- Fang, Wan-Yin,Dong, Tao,Han, Jia-Bin,Zha, Gao-Feng,Zhang, Cheng-Pan
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supporting information
p. 11502 - 11509
(2016/12/16)
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- Transition-Metal-Free N-Arylation of Pyrazoles with Diaryliodonium Salts
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A new synthetic method was developed for the N-arylation of pyrazoles using diaryliodonium salts. The transformation does not require any transition-metal catalyst and provides the desired N-arylpyrazoles rapidly under mild reaction condition in the presence of aqueous ammonia solution as a mild base without the use of inert atmosphere. The chemoselectivity of unsymmetric diaryliodonium salts was also explored with large number of examples.
- Gonda, Zsombor,Novák, Zoltán
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supporting information
p. 16801 - 16806
(2015/11/16)
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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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- Redox-controlled selectivity of C-H activation in the oxidative cross-coupling of arenes
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Gold brings us together: Taking advantage of the orthogonal reactivities of AuI and AuIII towards C-H activation of electron-poor and electron-rich arenes, respectively, a novel approach for the synthesis of biaryls through double C-H activation is proposed. Stoichiometric studies demonstrate that these oxidative couplings occur with high selectivity at low temperature. Copyright
- Cambeiro, Xacobe C.,Boorman, Tanya C.,Lu, Pengfei,Larrosa, Igor
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supporting information
p. 1781 - 1784
(2013/04/10)
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- Design of oligothiophene-based tetrazoles for laser-triggered photoclick chemistry in living cells
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A 405 nm light-activatable terthiophene-based tetrazole was designed that reacts with a fumarate dipolarophile with the second-order rate constant k 2 exceeding 103 M-1 s-1. The utility of this laser-activatable tetrazole in imaging microtubules in a spatiotemporally controlled manner in live cells was demonstrated.
- An, Peng,Yu, Zhipeng,Lin, Qing
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supporting information
p. 9920 - 9922
(2013/10/22)
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- Facile synthesis of Koser's reagent and derivatives from iodine or aryl iodides
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The first one-pot synthesis of neutral and electron-rich [hydroxy(tosyloxy)iodo]arenes (HTIBs) from iodine and arenes is presented, thereby avoiding the need for expensive iodine(III) precursors. A large set of HTIBs, including a polyfluorinated analogue, can be obtained from the corresponding aryl iodide under the same conditions. The reaction proceeds under mild conditions, without excess reagents, and is fast and high-yielding. Together, the two presented routes give access to a wide range of HTIBs, which are useful reagents in a variety of synthetic transformations.
- Merritt, Eleanor A.,Carneiro, Vania M. T.,Silva Jr., Luiz F.,Olofsson, Berit
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experimental part
p. 7416 - 7419
(2011/02/22)
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- Rapid microwave-promoted solvent-free synthesis of hypervalent iodine reagents
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Hypervalent hydroxy(sulfonyloxy)iodoarenes, hydroxy(phosphoryloxy) iodoarenes and bis(trifluoroactoxy)iodobenzene have been synthesised by a fast and convenient solvent-free ligand exchange reaction from the (diacetoxyiodo)arene under microwave irradiation, providing a simple method for the synthesis of these hypervalent iodine reagents in good yield and in a short time.
- Zhou, Zhongshi,He, Xuehan
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experimental part
p. 30 - 31
(2009/10/15)
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- Asymmetric cycloetherification based on a chiral auxiliary for 4-acyloxy-1-butene substrates during oxidation with iodosylbenzene via a 1,3-dioxan-2-yl cation
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Reaction of but-3-enyl camphanate and its derivatives with iodosylbenzene yielded tetrahydrofuran-3-yl camphanate with high diastereomeric ratio via a 1,3-dioxan-2-yl cation intermediate. The reaction using (1S)-camphanate as a chiral auxiliary preferentially gave (S)-3-acyloxytetrahydrofuran and (2S,3S)-3-acyloxy-2-silyltetrahydrofuran.
- Fujita, Morifumi,Ookubo, Yuuya,Sugimura, Takashi
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supporting information; body text
p. 1298 - 1300
(2009/09/08)
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- [Hydroxy(tosyloxy)iodo]benzene mediated α-azidation of ketones
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Reaction of various ketones with [hydroxy(tosyloxy)iodo]benzene (HTIB) followed by treatment of the α-tosyloxy ketones thus generated in situ with NaN3 offers a one-pot procedure for the synthesis of α-azido ketones. The HTIB used in this conversion may also be generated in situ by using iodosobenzene in combination with p-toluene-sulphonic acid.
- Prakash, Om,Pannu, Kamaljeet,Prakash, Richa,Batra, Anita
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p. 523 - 527
(2007/10/03)
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- Solvent-free reactions with hypervalent iodine reagents
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(Chemical Equation Presented) We describe solvent-free reactions for the synthesis of hypervalent iodine reagents and their use in solid-state reactions. Improved yields and higher purities of the products are observed.
- Yusubov, Mekhman S.,Wirth, Thomas
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p. 519 - 521
(2007/10/03)
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- Facile one-pot preparation of [hydroxy(sulfonyloxy)iodo]arenes from iodoarenes with MCPBA in the presence of sulfonic acids
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Various [hydroxy(sulfonyloxy)iodo]arenes were simply and efficiently obtained in high yields from the reaction of iodoarenes and MCPBA in the presence of sulfonic acids in a small amount of chloroform at room temperature, through a one-pot procedure. Georg Thieme Verlag Stuttgart.
- Yamamoto, Yukiharu,Togo, Hideo
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p. 2486 - 2488
(2007/10/03)
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- Straightforward syntheses of hypervalent iodine(III) reagents mediated by selectfluor
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(Chemical Equation Presented) Use of Selectfluor allows hypervalent iodine(III) species such as aryl iodine(III) difluoride, diacetate, and di(trifluoroacetate) and Koser's salt to be easily prepared. Aryl iodine(III) difluoride and diacetate can be synthesized from the corresponding arene and elemental iodine in one-pot procedures.
- Ye, Chengfeng,Twamley, Brendan,Shreeve, Jean'ne M.
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p. 3961 - 3964
(2007/10/03)
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- Rhodium versus ruthenium: Contrasting behaviour in the asymmetric transfer hydrogenation of α-substituted acetophenones
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The reduction of a number of α-substituted acetophenones has been achieved using both ruthenium(II)- and rhodium(III)-based asymmetric transfer hydrogenation catalysts employing formic acid as the hydrogen donor.
- Cross, David J.,Kenny, Jennifer A.,Houson, Ian,Campbell, Lynne,Walsgrove, Tim,Wills, Martin
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p. 1801 - 1806
(2007/10/03)
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- Aryliodonium derivatives of 2-amino-1,4-quinones: Preparation and reactivity
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The reaction of 2-amino-1,4-quinones with [(hydroxy)(tosyloxy)iodo]arenes affords stable 2-amino-3-aryliodonio-1,4- quinones in high yields. The latter, upon treatment with alkali, are converted to the corresponding zwitterionic 3-aryliodonio-1,4-quinone-2-imides. This new class of compounds exhibits an interesting reactivity: upon heating, aryl migration from iodine to nitrogen is observed, while photochemical reaction with aromatic compounds and 2,3-dihydrofuran leads to substitution products. Nucleophilic attack of sodium alkoxides on these zwitterions results in opening of the quinone ring affording synthetically interesting multifunctional products.
- Papoutsis, Ioannis,Spyroudis, Spyros,Varvoglis, Anastasios,Raptopoulou, Catherine P.
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p. 6097 - 6112
(2007/10/03)
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- NOVEL PENTAFLUOROPHENYL HYPERVALENT IODINE REAGENTS
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The novel C6F5I(OH)OTs has been synthesized and shown to undergo ligand exchange with C6H5I,iodonium ylide formation with dimedone and iodonium salt formation with anisole.
- Moriarty, Robert M.,Penmasta, Raju,Prakash, Indra
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p. 877 - 880
(2007/10/02)
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- Oxo-bridged Compounds of Iodine(III): Syntheses, Structure, and Properties of μ-Oxo-bis
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The title compound has been prepared by using several approaches.It reacts with both strong bases and acids and is an oxidant.Its crystal structure has been determined from four-circle diffractometer data (R=0.043).The primary iodine geometry is T-shaped o>, with shorter I-O (bridge) than I-O (acid) .Secondary bonds have I...O of 2.929(8) Angstroem to 3.273(8) Angstroem.
- Gallos, John,Varvoglis, Anastasios,Alcock, Nathaniel W.
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p. 757 - 764
(2007/10/02)
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- Iodonium salts
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Mono- or bis(iodonium salts) are produced in neutral organic solvents by the reaction of an [hydroxy (organosulfonyloxy)iodo]arene with a bis(triorganosilyl)arene, a bis(trihalosilyl)arene, or with a mono- or bis(triorganosilyl)heterocyclic compound, or a mono- or bis(trihalosilyl)heterocyclic. The iodonium salts are made under conditions of regiospecific control.
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