- Remote Substituents as Potential Control Elements for the Solid-State Structures of Hypervalent Iodine(III) Compounds
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Hypervalent iodine (HVI) compounds are very important selective oxidants often employed in organic syntheses. Most HVI compounds are strongly associated in the solid state involving interactions between the electropositive iodine centers and nearby electr
- Li, Guobi,Rheingold, Arnold L.,Protasiewicz, John D.
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supporting information
p. 7865 - 7875
(2021/05/26)
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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 0063-0064
(2020/12/31)
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- An Efficient Approach to Functionalized Indoles from λ3-Iodanes via Acyloxylation and Acyl Transfer
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Versatile role of λ3-iodanes has been identified between the reaction of hydroquinone and β-enaminones for the synthesis of 5-acyloxy-4-hydroxy indoles. The reaction is proposed to proceed through an intermolecular C?C bond formation, intramole
- Jeyakannu, Palaniraja,Chandru Senadi, Gopal,Chiang, Chun-Hsien,Kumar Dhandabani, Ganesh,Chang, Yu-Ching,Wang, Jeh-Jeng
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supporting information
p. 2911 - 2920
(2020/06/02)
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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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- λ3-Iodanes as Visible Light Photocatalyst in Thioacetalization of Aldehydes
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Introduction of an iodine(III) reagent as visible-light photocatalyst for chemoselective dithioacetalization has been the limelight of the current methodology. The mechanistic investigations reveal that the reactions proceeded via radical pathway upon lig
- Choudhuri, Khokan,Pramanik, Milan,Mal, Prasenjit
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supporting information
p. 4822 - 4826
(2019/07/31)
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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 0060
(2020/02/14)
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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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- Preparation method and device for iodobenzene dibenzoate derivative
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The invention relates to a preparation method and device for an iodobenzene dibenzoate derivative. The method includes the steps that 6 mmol of iodobenzene diacetate and 12 mmol of benzoic acid or a benzoic acid derivative or pivalic acid are added into a
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Paragraph 0020; 0021; 0022; 0023
(2017/02/09)
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- Synthesis of secondary amides from N-Substituted amidines by tandem oxidative rearrangement and isocyanate elimination
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In this work an efficient tandem process transforming N-substituted amidines into secondary amides has been described. The process involves N-acylurea formation by reaction of the substrate with bis(acyloxy)(phenyl)-λ3-iodane followed by isocyanate elimination. The periodinane reagents are obtained from the commercially available phenyl-iodine(III) diacetate [PhI(OAc)2, (PIDA)] by ligand exchange with carboxylic acids. The N-substituted amidine substrates are easily synthesized from readily available nitriles. The method is applicable for secondary amide synthesis, based on both aliphatic and (hetero)aromatic amines, including challenging amides consisting of sterically hindered acids and amines. Moreover, the protocol allows one to combine steric bulk with electron deficiency in the target amides (aniline based). Such compounds are difficult to synthesize efficiently based on classical condensation reactions involving carboxylic acids and amines. Overall, the synthetic protocol transforms a nitrile into a secondary amide in both aliphatic and (hetero)aromatic systems.
- Debnath, Pradip,Baeten, Mattijs,Lefvre, Nicolas,Van Daele, Stijn,Maes, Bert U. W.
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p. 197 - 209
(2015/03/03)
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- Regio- and stereoselective iodoacyloxylations of alkynes
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A new method for the regioselective and stereoselective iodoacyloxylation of alkynes has been developed. This protocol utilizes a combination of an iodobenzene dicarboxylate and iodine to functionalize a series of activated and unactivated alkynes in an entirely selective and predictable fashion. The resultant iodo-enol esters were subsequently coupled with boronic acids to afford tetrasubstituted alkene derivatives, which could be further converted to the corresponding 1,1-disubstituted acetophenone.
- Priebbenow, Daniel L.,Gable, Robert. W.,Baell, Jonathan
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p. 4412 - 4418
(2015/05/13)
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- Palladium catalyzed ortho-C-H-benzoxylation of 2-arylpyridines using iodobenzene dibenzoates
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A palladium-catalyzed ortho-C-H-benzoxylation of 2-arylpyridines using iodobenzene dibenzoates has been developed. The reaction employed the stable and easily accessible hypervalent iodine reagents as both benzoxylate source and oxidant which made the protocol simple and facile. It showed high regioselectivity and good functional group tolerance, and gave the mono-benzoxylation products in moderate to excellent yields.
- Zhang, Qian,Wang, Ying,Yang, Tingting,Li, Li,Li, Dong
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supporting information
p. 6136 - 6141
(2015/10/28)
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- Metal-free CH bond activation of branched aldehydes with a hypervalent iodine(III) catalyst under visible-light photolysis: Successful trapping with electron-deficient olefins
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Direct acyl radical formation of linear aldehydes (RCH2-CHO) and subsequent hydroacylation with electron-deficient olefins can be effected with various types of metal and nonmetal catalysts/reagents. In marked contrast however no successful reports on the use of branched aldehydes have been made thus far because of their strong tendency of generating alkyl radicals through the facile decarbonylation of acyl radicals. Here use of a hypervalent iodine(III) catalyst under visible light photolysis allows a mild way of generating acyl radicals from various branched aldehydes thereby giving the corresponding hydroacylated products almost exclusively. Another characteristic feature of this approach is the catalytic use of hypervalent iodine(III) reagent which is a rare example on the generation of radicals in hypervalent iodine chemistry.
- Moteki, Shin A.,Usui, Asuka,Selvakumar, Sermadurai,Zhang, Tiexin,Maruoka, Keiji
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supporting information
p. 11060 - 11064
(2015/03/30)
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- Alkene Oxyalkylation Enabled by Merging Rhenium Catalysis with Hypervalent Iodine(III) Reagents via Decarboxylation
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Rhenium-catalyzed oxyalkylation of alkenes is described, where hypervalent iodine(III) reagents derived from widely occurring aliphatic carboxylic acids were used as, for the first time, not only an oxygenation source but also an alkylation source via decarboxylation. The reaction also features a wide substrate scope, totally regiospecific difunctionalization, mild reaction conditions, and ready availability of both substrates. Mechanistic studies revealed a decarboxylation/radical-addition/cation-trapping cascade operating in the reaction.
- Wang, Yin,Zhang, Lei,Yang, Yunhui,Zhang, Ping,Du, Zhenting,Wang, Congyang
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supporting information
p. 18048 - 18051
(2014/01/06)
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- α-Acyloxynitroso dienophiles in [4+2] hetero Diels-Alder cycloadditions: mechanistic insights
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α-Acyloxynitroso derivatives are a class of heterodienophiles leading to valuable 3,6-dihydro-1,2-oxazines or the corresponding aminoalcohols in good yields. The discovery that a β-oxygenated moiety led to a domino [4+2] cycloaddition/σN-O bond cleavage in the presence of a catalytic amount of Lewis acid was investigated in detail, through kinetic profiling of the reaction both in the absence and presence of a promoter. These studies showed that the role of the Lewis acid was to accelerate the σN-O bond cleavage thereby promoting a highly reproducible sequence. In addition, our preliminary results on an asymmetric version of this domino sequence are reported.
- Calvet, Géraldine,Coote, Susannah C.,Blanchard, Nicolas,Kouklovsky, Cyrille
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supporting information; experimental part
p. 2969 - 2980
(2010/06/20)
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- Direct conversion of secondary phosphine oxides and h-phosphinates with [Di(acyloxy)iodo]benzenes to phosphinic and phosphonic amides
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The reaction of [di(acyloxy)iodo]- benzene with secondary phosphine oxides or H-phosphinates in the presence of primary or secondary amines allows one to obtain phosphinic or phosphonic acids amides in the one-pot process. We take advantage of the strong acylating system DAIB/R2P(O)H to phosphinylation of amines. However, the reaction mechanism is multipathway and causes yields of phosphinic or phosphonic acids amides to be moderate. When the concentration of amines is low, the intermolecular process plays a main role leading to the formation of carboxylic amides through mixed phosphoric-carboxylic anhydride, and also in the low concentration of amines, tetrahydrofuran effectively competes with the amines in the nucleophilic attack on the acylating intermediates.
- Hubacz, Anna,Makowiec, Slawomir
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experimental part
p. 81 - 86
(2009/09/25)
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- Solution structure of some λ3 iodanes: An 17O NMR and DFT study
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(Figure Presented) The structure of a series of I-O bonded bis(acyloxy)iodoarenes and benzoiodoxolones in chloroform solution has been investigated by 17O NMR spectroscopy and by density functional theory (DFT) calculations, employing the PBE0 functional together with the LANL2DZ basis set extended with polarization (d) and diffuse (p) functions. This combined approach allowed us to ascertain that, although these classes of λ3 iodanes maintain in chloroform solution their solid state "T-shaped" structure, a degenerate [1,3] sigmatropic shift of iodine between the two oxygens of the acyloxy groups occurs in solution. The energy barrier involved in this process differs in the two classes, thus causing significant differences in the 17O NMR spectra, at room temperature, of the two classes of compounds.
- Mocci, Francesca,Uccheddu, Gianluca,Frangia, Angelo,Cerioni, Giovanni
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p. 4163 - 4168
(2008/02/05)
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- MERCURY MEDIATED SYNTHESIS OF BIS(CARBOXY)IODOBENZENES
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Iodobenzene dibenzoates and acetoxylates can be conveniently prepared from iodobenzene dichloride and the corresponding mercuric carboxylate generated in situ.Especially noteworthy is the high yield preparation of bis(trifluoroacetoxy)iodobenzene.
- Taylor, Richard T.,Stevenson, Thomas A.
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p. 2033 - 2036
(2007/10/02)
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