- 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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Read Online
- Organoiodine-catalyzed oxidative spirocyclization of phenols using peracetic acid as a green and economic terminal oxidant
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The use of peracetic acid as a green and economical terminal oxidant in fluoroalcohol solvents could provide a practical iodoarene-catalyzed oxidation of phenols to give spirodienones. Acetic acid and water were the only co-products and waste, and thus th
- Minamitsuji, Yutaka,Kato, Daishi,Fujioka, Hiromichi,Dohi, Toshifumi,Kita, Yasuyuki
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Read Online
- Photocatalytic Fluoro Sulfoximidations of Styrenes
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Reactions of difluoroiodotoluene with NH-sulfoximines provide new hypervalent iodine(III) reagents, which photocatalytically transfer a fluoro and a sulfoximidoyl group onto styrenes with high regioselectivity. The substrate scope is broad with respect to
- Bolm, Carsten,Ma, Ding,Tu, Yongliang,Wang, Chenyang
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Read Online
- 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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- Method for producing hypervalent iodine compound
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The invention provides a method for producing a hypervalent iodine compound; the method is more effective than the prior art, improves yield while reducing reaction time, and is more suitable for industrial application.
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Paragraph 0065-0066
(2020/12/31)
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- The Role of Iodanyl Radicals as Critical Chain Carriers in Aerobic Hypervalent Iodine Chemistry
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Selective O2 utilization remains a substantial challenge in synthetic chemistry. Biological small-molecule oxidation reactions often utilize aerobically generated high-valent catalyst intermediates to effect substrate oxidation. Available synthetic methods for aerobic oxidation catalysis are largely limited to substrate functionalization chemistry by low-valent catalyst intermediates (i.e., aerobically generated Pd(II) intermediates). Motivated by the need for new chemical platforms for aerobic oxidation catalysis, we recently developed aerobic hypervalent iodine chemistry. Here, we report that in contrast to the canonical two-electron oxidation mechanisms for the oxidation of organoiodides, the developed aerobic hypervalent iodine chemistry proceeds via a radical chain mechanism initiated by the addition of aerobically generated acetoxy radicals to aryl iodides. Despite the radical chain mechanism, aerobic hypervalent iodine chemistry displays substrate tolerance similar to that observed with traditional terminal oxidants, such as peracids. We anticipate that these insights will enable new sustainable oxidation chemistry via hypervalent iodine intermediates. O2 is routinely utilized in biological catalysis to generate high-valent catalyst intermediates that engage in substrate oxidation chemistry. Analogous synthetic chemistry via aerobically generated high-valent intermediates would enable new sustainable synthetic methods but is largely unknown because of the challenges in selective O2 utilization. We have developed aerobic hypervalent iodine chemistry as a platform for coupling O2 reduction with a diverse set of substrate functionalization mechanisms. Many of the synthetic applications of hypervalent iodine reagents rely on selective two-electron oxidation-reduction chemistry. Here, we report that one-electron oxidation reactions pathways via iodanyl radical intermediates are critical in aerobic hypervalent iodine chemistry. The new appreciation for the critical role that iodanyl radicals can play in the synthesis of hypervalent iodine compounds will provide new opportunities in sustainable oxidation catalysis. Aerobic hypervalent iodine chemistry provides a strategy for coupling the one-electron chemistry of O2 with two-electron processes typical of organic synthesis. We show that in contrast to the canonical two-electron oxidation of aryl iodides, aerobic synthesis proceeds by a radical chain process initiated by the addition of aerobically generated acetoxy radicals to aryliodides to generate iodanyl radicals. Robustness analysis reveals that the developed aerobic oxidation chemistry displays substrate tolerance similar to that observed in peracid-based methods and thus holds promise as a sustainable synthetic method.
- Hyun, Sung-Min,Yuan, Mingbin,Maity, Asim,Gutierrez, Osvaldo,Powers, David C.
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supporting information
p. 2388 - 2404
(2019/09/12)
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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 0071-0072
(2019/01/15)
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- Iodosylbenzene Coordination Chemistry Relevant to Metal-Organic Framework Catalysis
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Hypervalent iodine compounds formally feature expanded valence shells at iodine. These reagents are broadly used in synthetic chemistry due to the ability to participate in well-defined oxidation-reduction processes and because the ligand-exchange chemist
- Cardenal, Ashley D.,Maity, Asim,Gao, Wen-Yang,Ashirov, Rahym,Hyun, Sung-Min,Powers, David C.
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supporting information
p. 10543 - 10553
(2019/09/13)
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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 0066
(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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- Synthesis of 2-Quinolinones via a Hypervalent Iodine(III)-Mediated Intramolecular Decarboxylative Heck-Type Reaction at Room Temperature
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A hypervalent iodine(III)-mediated intramolecular decarboxylative Heck-type reaction of 2-vinyl-phenyl oxamic acids has been developed. The unique ring-strain-enabled radical decarboxylation mechanism is preliminarily revealed. This protocol features metal-free reaction conditions and operational simplicity, allowing the lactamization of 2-vinylanilines using a readily accessible carbonyl source and the synthesis of various 2-quinolinones with excellent chemoselectivity at room temperature.
- Fan, Huaqiang,Pan, Peng,Zhang, Yongqiang,Wang, Wei
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supporting information
p. 7929 - 7932
(2019/01/04)
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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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- Synthesis method of 5-HT2C receptor-specific PET radiotracer
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The present invention relates to a synthesis method of a [^(18)F]5-fluoro-4-(((R)-1-(3-fluorophenyl)propan-2-yl)oxy)-2-((R)-2-methylpiperazin-1-yl)pyrimidin compound which is used as a 5-HT_(2c) receptor-specific radiotracer for positron emission tomograp
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Paragraph 0104; 0105; 0108
(2018/05/03)
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- Preparation method of p-methyl iodobenzene diacetate
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The invention relates to a preparation method of p-methyl iodobenzene diacetate. P-methyl iodobenzene and glacial acetic acid are added to a round-bottom flask, acetic anhydride is added after dissolution, the round-bottom flask is placed in an oil bath pan at 50 DEG C for magnetic stirring, NaBO3.4H2O is added, and the mixture is heated to react for 24 h. After the reaction ends, the product is left to stand, taken out and cooled to the room temperature, distilled water is added, suction filtration is performed, washing and extraction are performed with DCM 3 times, filtrate is collected, organic phases are mixed, drying is performed with anhydrous Na2SO4, filtration is performed, a solvent is removed, diethyl ether is added for cooling crystallization, white crystals separate out, suction filtration and drying are performed, and an iodobenzene diacetate derivative is obtained. The method adopts mild reaction conditions, has high selectivity, has the yield of 92% and is environmentally friendly.
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Paragraph 0011; 0012; 0013; 0014
(2018/05/16)
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- Synthesis of O -Aroyl- N, N -dimethylhydroxylamines through Hypervalent Iodine-Mediated Amination of Carboxylic Acids with N, N -Dimethylformamide
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An efficient protocol for the synthesis of O -aroyl- N, N -dimethylhydroxylamines, which are important electrophilic amination reagents, is described. The reaction between carboxylic acids and N, N -dimethylformamide is mediated by hypervalent iodine and
- Zhang, Chuancheng,Yue, Qiang,Xiao, Zhen,Wang, Xianglan,Zhang, Qian,Li, Dong
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supporting information
p. 4303 - 4308
(2017/09/13)
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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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- 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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- Geminal difunctionalization of α-diazo arylmethylphosphonates: Synthesis of fluorinated phosphonates
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A general approach towards diverse fluorinated phosphonates via geminal difunctionalization reactions of α-diazo arylmethylphosphonates is described. The diazo functionality (RR′CN2) is successfully converted to RR′CF2, RR′CHF, RR′CFBr or RR′CFNR′′2 groups by employing different fluorination reagents. A variety of fluorinated organophosphorus compounds were readily accessed in good to excellent yields from a common type of precursor.
- Zhou, Yujing,Zhang, Yan,Wang, Jianbo
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p. 10444 - 10453
(2016/11/18)
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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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- Tandem catalytic C(sp3)-H amination/sila-sonogashira-hagihara coupling reactions with iodine reagents
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A new tandem C-N and C-C bond-forming reaction has been achieved through RhII/Pd0 catalysis. The sequence first involves an iodine(III) oxidant, then the in situ generated iodine(I) by-product is used as a coupling partner. The overall process demonstrates the synthetic value of iodoarenes produced in trivalent iodine reagent mediated oxidations. I(003) is a double agent: A tandem C-N and C-C bond-forming reaction has been achieved through RhII/Pd0 catalysis. The sequence first involves an iodine(III) oxidant, then the in situ generated iodine(I) by-product is used as a coupling partner. The overall process affords complex building blocks with high yields, and demonstrates the synthetic value of iodoarenes produced in trivalent iodine reagent mediated oxidations.
- Buendia, Julien,Darses, Benjamin,Dauban, Philippe
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supporting information
p. 5697 - 5701
(2015/06/16)
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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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- Diversity-oriented approach to CF3CHF-, CF3CFBr-, CF3CF2-, (CF3)2CH-, and CF3(SCF3)CH-substituted arenes from 1-(Diazo-2,2,2-trifluoroethyl)arenes
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Arenes substituted with perfluoroalkyl groups are attractive targets for drug and agrochemical development. Exploiting the carbenic character of donor/acceptor diazo compounds, a diversity-oriented synthesis of perfluoroalkylated arenes, for late stage fluorofunctionalization, is described. The reaction of 1-(diazo-2,2,2-trifluoroethyl)arenes with HF, F/Br, F2, CF3H, and CF3SH sources give direct access to a variety of perfluoroalkyl-substituted arenes presenting with incremental fluorine content. The value of this approach is also demonstrated for radiochemistry and positron emission tomography with the [18F]-labeling of CF3CHF-, CF3CBrF-, and CF3CF2-arenes from [18F]fluoride.
- Emer, Enrico,Twilton, Jack,Tredwell, Matthew,Calderwood, Samuel,Collier, Thomas Lee,Ligault, Benot,Taillefer, Marc,Gouverneur, Vronique
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supporting information
p. 6004 - 6007
(2015/01/09)
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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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- Synthesis and reactivity of aryl(alkynyl)iodonium salts
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The first practical, yet simple, preparation of aryl(alkynyl)iodonium trifluoroacetate salts is described. The generic nature of this synthetic method has allowed the production of a range of aryl(alkynyl)iodonium trifluoroacetate salts with independent variation of both the alkynyl and aryliodo groups in yields of 30-85 %. Application of these new reagents to the synthesis of a series of 2-arylfuro[3,2-c]pyridines (40-64 %) highlights the potential of this class of materials as precursors to bioactive heterocyclic structures. These experiments have also demonstrated that, in this case, the effect of the aryliodo group on the reaction is negligible.
- Dixon, Luke I.,Carroll, Michael A.,Gregson, Thomas J.,Ellames, George J.,Harrington, Ross W.,Clegg, William
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supporting information
p. 2334 - 2345
(2013/05/21)
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- Metal-free direct oxidative intermolecular diarylation of anilides at ambient temperature assisted by cascade selective formation of C-C and C-N bonds
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A new atom-economical process of direct oxidative intermolecular functionalization of aniline derivatives by simple arenes was developed. The products were formed in a highly regioselective manner under metal-free conditions at ambient temperature. The Royal Society of Chemistry 2012.
- Samanta, Rajarshi,Lategahn, Jonas,Antonchick, Andrey P.
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supporting information; experimental part
p. 3194 - 3196
(2012/05/04)
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- Simple and practical method for preparation of [(diacetoxy)iodo]arenes with iodoarenes and m-chloroperoxybenzoic acid
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Various [(diacetoxy)iodo]arenes bearing 4-methylphenyl, phenyl, 4-nitrophenyl, 3-nitrophenyl, 4-cyanophenyl, 4-bromophenyl, 4- methoxycarbonyphenyl, 3,5-bis(trifluoromethyl)phenyl, and 4-(N,N,N- trimethylammonium)methylphenyl groups were efficiently prepared by the treatment of iodoarenes with m-chloroperoxybenzoic acid in acetic acid. The great advantage of the present method is the easy preparation and isolation of [(diacetoxy)-iodo]arenes bearing electron-withdrawing groups, such as 4-nitro, 4-cyano, 4-methoxycarbonyl, and 3,5-bis(trifluoromethyl) groups, on the aromatic ring.
- Iinuma, Masataka,Moriyama, Katsuhiko,Togo, Hideo
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p. 2663 - 2666,4
(2012/12/12)
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- Approach to the synthesis of indoline derivatives from diaryliodonium salts
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An effective method of constructing the indoline moiety via intramolecular nucleophilic ring closure of a diaryliodonium salt is described. Diacetoxyiodoarene compounds (1a-1e) were converted into intermediate Koser's reagent and coupled with arylstannanes (7-10) to form diaryliodonium salts (11a-14e). Indoline compounds with different N-protecting groups, 15, 16, 17, and 18, were synthesized in higher yields by treating salts (11a-14e) with Cs2CO3 and TEMPO. Regardless of the electronic environment of five para-substituted iodoarenes and the natures of four N-protected arylstannane groups, the conversion proceeded well to afford corresponding indolines in yields of 72-84 and 70-84%, respectively.
- Landge, Kamalkishor P.,Jang, Keun Sam,Lee, Sang Yeul,Chi, Dae Yoon
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experimental part
p. 5705 - 5713
(2012/09/07)
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- Direct arylation of benzoxazole C-H bonds with iodobenzene diacetates
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A Pd (OAc)2-catalyzed direct arylation of benzoxazole C-H bonds has been achieved with iodobenzene diacetates as the arylation reagent in moderate to good yields. The procedure tolerates a series of functional groups, such as methoxy, nitro, cyano, chloro, and bromo groups.
- Yu, Peng,Zhang, Guangyou,Chen, Fan,Cheng, Jiang
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supporting information; experimental part
p. 4588 - 4590
(2012/09/22)
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- 4-ARYLOXYQUINOLIN-2(1H)-ONES AS MTOR KINASE AND PI3 KINASE INHIBITORS, FOR USE AS ANTI-CANCER AGENTS
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4-aryloxyquinolin-2(1H)-ones as mtor kinase and PI3 kinase inhibitors, for use as anti-cancer agents. Compounds of the formula I and pharmaceutically acceptable salts thereof, wherein A, B, R1, R2, R3, R4, R5, R6, and R7 are defined as set forth herein are disclosed. Also disclosed are pharmaceutical compositions comprising the compounds of the invention and a pharmaceutically acceptable carrier, methods of making the compounds of the invention and methods of using the compounds for inhibiting mTOR and PI3 kinases and for treating cancers.
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Page/Page column 60
(2010/04/06)
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- New and direct approach to hypervalent iodine compounds from arenes and iodine. straightforward synthesis of (diacetoxyiodo)arenes and diaryliodonium salts using potassium μ-peroxo-hexaoxodisulfate
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The reaction of arenes with elemental iodine, acetic acid, and potassium μ-peroxo-hexaoxodisulfate (K2S2O8) in the presence of concentrated sulfuric acid, efficiently generated the corresponding (diacetoxyiodo)arenes in good yields. Diaryliodonium triflates were directly synthesized by reaction of arenes with elemental iodine in good yields by using K2S2O8, AcOH, and TfOH. Diaryliodonium tosylates were also prepared from arenes and elemental iodine by using K 2S2O8, AcOH, H2SO4, and TsOH. The procedure involved mild conditions and a straightforward one-pot synthesis.
- Hossain, Md. Delwar,Kitamura, Tsugio
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experimental part
p. 2213 - 2219
(2009/08/08)
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- Direct, easy, and scalable preparation of (diacetoxyiodo)arenes from arenes using potassium peroxodisulfate as the oxidant
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The reaction of arenes with potassium peroxodisulfate, elemental iodine, and acetic acid in the presence of concd sulfuric acid, efficiently generates the corresponding (diacetoxyiodo)arenes in good yields, providing an easy, safe, and effective method for preparing (diacetoxyiodo)arenes from arenes and iodine.
- Hossain, Md. Delwar,Kitamura, Tsugio
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p. 7889 - 7891
(2007/10/03)
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- Unexpected, drastic effect of triflic acid on oxidative diacetoxylation of iodoarenes by sodium perborate. A facile and efficient one-pot synthesis of (diacetoxyiodo) arenes
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An easy, safe, and effective method for preparing (diacetoxyiodo)arenes from iodoarenes is presented. Addition of trifluoromethanesulfonic acid (triflic acid) as a promoter causes a drastic increase in the yield of (diacetoxyiodo)arenes in the reaction of iodoarenes with sodium perborate. The reaction of the iodoarenes with sodium perborate in acetic acid in the presence of triflic acid at 40-45 °C efficiently generates the corresponding (diacetoxyiodo)arenes in high yields within short time.
- Hossain, Md. Delwar,Kitamura, Tsugio
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p. 6984 - 6986
(2007/10/03)
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- Alternative, easy preparation of (diacetoxyiodo)arenes from iodoarenes using potassium peroxodisulfate as the oxidant
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An easy, safe and effective method for preparing (diacetoxyiodo)arenes [ArI(OAc)2], from iodoarenes is presented in this paper, using potassium peroxodisulfate as the oxidant. This procedure avoids the use of high temperature and severe reaction conditions. The reaction of the iodoarenes with potassium peroxodisulfate in acetic acid in the presence of concentrated sulfuric acid or trifluoromethane sulfonic acid at room temperature, efficiently generates the corresponding (diacetoxyiodo)arenes in high yield in a short reaction time. Georg Thieme Verlag Stuttgart.
- Hossain, Md. Delwar,Kitamura, Tsugio
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p. 1932 - 1934
(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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- 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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- Enantioselective epoxidation of (Z)-stilbene using a chiral Mn(III)-salen complex: Effect of immobilisation on MCM-41 on product selectivity
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Manganese-exchanged Al-MCM-41 modified by the chiral salen ligand [(R,R)-(-)-N,N′-bis(3,5-di-tert-butyl-salicylidene)cyclohexane-1,2-diamine ] has been investigated as a heterogeneous catalyst for the enantioselective epoxidation of (Z)-stilbene using iodosylbenzene as oxygen donor, with particular interest in the effect of reaction conditions on the cis:trans ratio of the epoxide product. Immobilisation of the chiral Mn-salen complex in Al-MCM-41 increases the cis:trans ratio of the epoxide product when compared to the non-immobilised complex under the same conditions. Increasing the level of Mn-exchange in the Al-MCM-41 increases the amount of trans-epoxide, whereas increasing the iodosylbenzene:substrate ratio increases the amount of cis product formed. Increasing the reaction temperature also increases the amount of trans-epoxide for the homogeneous Mn-complex under the same conditions. A series of experiments is described in which the external ion-exchange sites on Al-MCM-41 are preferentially silanised, which enables the cis/trans selectivity for external and internal sites to be determined. Mn-salen immobilised on the external surface of Al-MCM-41 gives the same cis:trans ratio as that observed with the non-immobilised Mn-salen complex in solution, whereas Mn-salen immobilised within the pores gives the cis-epoxide preferentially. The enantioselection of the immobilised chiral Mn-salen complex is shown to decrease with reaction time at -10 °C, but the cis:trans epoxide ratio remains unchanged; whereas for the non-immobilised complex in solution the enantioselection is independent of reaction time. Iodobenzene, a decomposition product formed from iodosylbenzene, is found to act as a poison for the immobilised catalyst, leading to a slower reaction and lower enantioselection.
- Piaggio, Paola,McMorn, Paul,Murphy, Damien,Bethell, Donald,Bulman Page, Philip C.,Hancock, Frederick E.,Sly, Christopher,Kerton, Owain J.,Hutchings, Graham J.
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p. 2008 - 2015
(2007/10/03)
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- Reactivity of arenes in substitution and additiopn reactions
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The reactivity of arenes with 4-methylquinoline (substitution) as a typical heteroaromatic base and phenyl vinyl sulfone (addition) as a typical activated olefin has been studied under thermal and irradiation conditions.The results suggest that electron-withdrawing groups on the aromatic ring in arenes are detrimental to reactions.The crystal structures of arenes 10 and 1e are reported.
- Togo, Hideo,Taguchi, Rie,Yamaguchi, Kentaro,Yoikoyama, Masataka
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p. 2135 - 2140
(2007/10/02)
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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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