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Applications of hypervalent iodine(III) reagents in constructing ortho-iodo aromatic ethers
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
p. 818 - 822
(2021/04/22)

Synthesis of Diverse Aryliodine(III) Reagents by Anodic Oxidation?
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
supporting information
p. 627 - 632
(2021/02/12)

Preparation and Synthetic Applicability of Imidazole-Containing Cyclic Iodonium Salts
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.
p. 7163 - 7178
(2021/05/29)

Method for producing hypervalent iodine compound
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 0047-0060

(2020/12/31)

A trivalent hypervalent iodine compound using hypochlorite (by machine translation)
[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 0057

(2020/02/14)

The Role of Iodanyl Radicals as Critical Chain Carriers in Aerobic Hypervalent Iodine Chemistry
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.
supporting information
p. 2388 - 2404
(2019/09/12)

Continuous-Flow Electrochemical Generator of Hypervalent Iodine Reagents: Synthetic Applications
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
supporting information
p. 9811 - 9815
(2019/06/24)

SYNTHESIS OF HYPERVALENT IODINE REAGENTS WITH DIOXYGEN
Methods of synthesis of hypervalent iodine reagents and methods for oxidation of organic compounds are disclosed.
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Paragraph 0065-0067; 0193-0194

(2019/01/15)

Safer Synthesis of (Diacetoxyiodo)arenes Using Sodium Hypochlorite Pentahydrate
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
p. 14262 - 14268
(2018/11/23)

Oxidase catalysis via aerobically generated hypervalent iodine intermediates
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.
p. 200 - 204
(2018/02/06)

Heterocyclic ring aromatic ether compound and synthesis method thereof
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)

Synthesis of O -Aroyl- N, N -dimethylhydroxylamines through Hypervalent Iodine-Mediated Amination of Carboxylic Acids with N, N -Dimethylformamide
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
supporting information
p. 4303 - 4308
(2017/09/13)

Stereoselective Ketone Rearrangements with Hypervalent Iodine Reagents
The first stereoselective version of an iodine(III)-mediated rearrangement of arylketones in the presence of orthoesters is described. The reaction products, α-arylated esters, are very useful intermediates in the synthesis of bioactive compounds such as ibuprofen. With chiral lactic acid-based iodine(III) reagents product selectivities of up to 73 % ee have been achieved.
Malmedy, Florence,Wirth, Thomas
supporting information
p. 16072 - 16077
(2016/10/30)

Generation of Aryl Radicals through Reduction of Hypervalent Iodine(III) Compounds with TEMPONa: Radical Alkene Oxyarylation
A novel method for selective generation of aryl radicals from diaryliodonium salts and iodanylidene malonates with sodium 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPONa) as a single-electron transfer (SET) reducing reagent is described. In the presence of various alkenes, aryl radicals formed after SET-reduction of hypervalent iodine compounds undergo alkene addition and the adduct radicals that are thus generated are efficiently trapped by the concomitantly generated TEMPO radical to eventually afford oxyarylated products in moderate to very good yields. The efficiency of aryl radical generation of various iodine(III) reagents is studied and the generation of an iodanylidene malonate aryl radical is also investigated by computational methods.
Hartmann, Marcel,Li, Yi,Mück-Lichtenfeld, Christian,Studer, Armido
p. 3485 - 3490
(2016/03/05)

Synthesis of secondary amides from N-Substituted amidines by tandem oxidative rearrangement and isocyanate elimination
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.
supporting information
p. 197 - 209
(2015/03/03)

Microwave-assisted synthesis of fulleropyrazolines/fulleroisoxazolines mediated by (diacetoxyiodo)benzene: A rapid and green procedure
Microwave as a green, rapid and effective procedure has been applied to the synthesis of fulleropyrazolines/fulleroisoxazolines. The reaction mixtures containing substituted phenylhydrazones/oximes, C60 and PhI(OAc) 2 allowed to achieve products at room temperature in a good yield and short time without any side product.
Safaei-Ghomi, Javad,Masoomi, Reihaneh
p. 2954 - 2960
(2014/01/06)

Synthesis and reactivity of aryl(alkynyl)iodonium salts
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
supporting information
p. 2334 - 2345
(2013/05/21)

Direct arylation of benzoxazole C-H bonds with iodobenzene diacetates
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
supporting information; experimental part
p. 4588 - 4590
(2012/09/22)

Simple and practical method for preparation of [(diacetoxy)iodo]arenes with iodoarenes and m-chloroperoxybenzoic acid
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
p. 2663 - 2666,4
(2012/12/12)

Study on the reactive transient α-λ3-iodanyl- acetophenone complex in the iodine(III)/PhI(I) catalytic cycle of iodobenzene-catalyzed α-acetoxylation reaction of acetophenone by electrospray ionization tandem mass spectrometry
RATIONALE Hypervalent iodine compounds are important and widely used oxidants in organic chemistry. In 2005, Ochiai reported the PhI-catalyzed α-acetoxylation reaction of acetophenone by the oxidation of PhI with m-chloroperbenzoic acid (m-CPBA) in acetic acid. However, until now, the most critical reactive α-λ3-iodine alkyl acetophenone intermediate (3) had not been isolated or directly detected. METHODS Electrospray ionization tandem mass spectrometry (ESI-MS/MS) was used to intercept and characterize the transient reactive α-λ3- iodine alkyl acetophenone intermediate in the reaction solution. RESULTS The trivalent iodine species was detected when PhI and m-CPBA in acetic acid were mixed, which indicated the facile oxidation of a catalytic amount of PhI(I) to the iodine(III) species by m-CPBA. Most importantly, 3·H+ was observed at m/z 383 from the reaction solution and this ion gave the protonated α-acetoxylation product 4·H+ at m/z 179 in MS/MS by an intramolecular reductive elimination of PhI. CONCLUSIONS These ESI-MS/MS studies showed the existence of the reactive α-λ3-iodine alkyl acetophenone intermediate 3 in the catalytic cycle. Moreover, the gas-phase reactivity of 3·H+ was consistent with the proposed solution-phase reactivity of the α-λ3-iodine alkyl acetophenone intermediate 3, thus confirming the reaction mechanism proposed by Ochiai. Copyright
Wang, Hao-Yang,Zhou, Juan,Guo, Yin-Long
experimental part
p. 616 - 620
(2012/06/16)

Study of Co(AAOPD) and Cu(AAOPD) schiff-base catalysts effect in oxidation oximes and carboxylic acids derivatives
Oximes and carboxylic acids derivatives have a wide range in medical, pharmaceutical, agriculture industrials. Thus they have significant effects on these fields. Base-promoted or (RC=N-) groups of cobalt and nickel groups. These were examined for oxidative process of oximes and carboxylic acids. This process is absolutely selective and in this procedure oximes transforms to aldehyde and ketone derivatives with high yield, without more oxidative process on Aldehyde group. In this mechanism high amounts of various oximes transforms into carbonyi group. However, obtained results showed that oxidative process for oximes and carboxylic acid with presence of Base-Promoted such as Co(AAOPD) and Cu(AAOPD) because of higher speed and yield. For more evaluation of reaction progress and identification of products through different methods like were used: Thin Layer Chromatography (TLC), Gas Chromatography, FT-IR, UV-Vis and elemental analysis. Carboxylic acids;. Carboxylic acids;. Oximes;. Schiff-Base.
Soleymani, Reza,Taheri, Milad,HOSEYNALIBEYGl, Marziye,Daryani, Mehdi
p. 857 - 866,10
(2020/08/24)

4-ARYLOXYQUINOLIN-2(1H)-ONES AS MTOR KINASE AND PI3 KINASE INHIBITORS, FOR USE AS ANTI-CANCER AGENTS
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)

The continuous-flow synthesis of ibuprofen
Let relief flow forth I A three-step, continuous-flow synthesis of ibuprofen was accomplished using a simplified microreactor. By designing a synthesis in which excess reagents and byproducts are compatible with downstream reactions, no intermediate purification or isolation steps are required.
Bogdan, Andrew R.,Poe, Sarah L.,Kubis, Daniel C.,Broadwater, Steven J.,McQuade, D. Tyler
supporting information; experimental part
p. 8547 - 8550
(2009/12/31)

The reaction of terminal alkynes with PhI(OAc)2: a convenient procedure for the preparation of α-acyloxy ketones
Treatment of terminal alkynes with PhI(OAc)2 in different acids at 70 °C provided the corresponding α-acyloxy ketones in good to excellent yields. A plausible mechanism has been proposed based on the experimental results.
Mo, Dong-Liang,Dai, Li-Xin,Hou, Xue-Long
body text
p. 5578 - 5581
(2011/02/22)

Clean and highly selective oxidation of alcohols by the Phl(OAc) 2/Mn(TPP)CN/lm catalytic system
An efficient method for the oxidation of alcohols is presented. Using catalytic amounts of manganese porphyrin [Mn(TPP)CN] in combination with (diacetoxyiodo)benzene (Phl(OAc)2) allows the conversion of benzylic and primary aliphatic and aromatic alcohols into the corresponding aldehydes, and secondary alcohols to ketones as the sole products. This method provides a cost-effective and environmentally friendly oxidation procedure due to the utilisation of less toxic Phl(OAc)2 and biologically relevant manganese porphyrins. The amounts of the products (%) and the selectivities are very dependent upon the nature of the metalloporphyrin catalysts and also upon the electronic and steric properties of the starting alcohols.
Karimipour, Gholam Reza,Shadegan, Hamid Asadpour,Ahmadpour, Roxana
p. 252 - 256
(2008/02/08)

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
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
experimental part
p. 2213 - 2219
(2009/08/08)

Chemistry of 4-alkylaryloxenium ion "precursors": Sound and fury signifying something?
(Chemical Equation Presented) Quinol esters 2b, 2c, and 3b and sulfonamide 4c were investigated as possible precursors to 4-alkylaryloxenium ions, reactive intermediates that have not been previously detected. These compounds exhibit a variety of interesting reactions, but with one possible exception, they do not generate oxenium ions. The 4-isopropyl ester 2b predominantly undergoes ordinary acid- and base-catalyzed ester hydrolysis. The 4-tert-butyl ester 2c decomposes under both acidic and neutral conditions to generate tert-butanol and 1-acetyl-1,4-hydroquinone, 8, apparently by an SN1 mechanism. This is also a minor decomposition pathway for 2b, but the mechanism in that case is not likely to be SN1. Decomposition of 2c in the presence of N 3- leads to formation of the explosive 2,3,5,6-tetraazido-1,4-benzoquinone, 14, produced by N3 -induced hydrolysis of 8, followed by a series of oxidations and nucleophilic additions by N3 . No products suggestive of N3--trapping of an oxenium ion were detected. The 4-isopropyl dichloroacetic acid ester 3b reacts with N3- to generate the two adducts 2-azido-4-isopropylphenol, 5b, and 3-azido-4-isopropylphenol, 11b. Although 5b is the expected product of N3- trapping of the oxenium ion, kinetic analysis shows that it is produced by a kinetically bimolecular reaction of N3- with 3b. No oxenium ion is involved. The sulfonamide 4c predominantly undergoes a rearrangement reaction under acidic and neutral conditions, but a minor component of the reaction yields 4-tert-butylcresol, 17, and 2-azido-4-tert-butylphenol, 5c, in the presence of N3-. These products may indicate that 4c generates the oxenium ion 1c, but they are generated in very low yields (ca. 10%) so it is not possible to definitively conclude that 1c has been produced. If 1c has been generated, the N3--trapping data indicate that it is a very short-lived and reactive species in H2O. Comparisons with similarly reactive nitrenium ions indicate that the lifetime of 1c is ca. 20-200 ps if it is generated, so it must react by a preassociation process. Density functional theory calculations at the B3LYP/6-31G*//HF/6-31G* level coupled with kinetic correlations also indicate that the aqueous solution lifetimes of 1a-c are in the picosecond range.
Novak, Michael,Brinster, Aaron M.,Dickhoff, Jill N.,Jones, Matthew P.,Leopold, Samuel H.,Vollman, Andrew T.,Wang, Yue-Ting,Glover, Stephen A.
p. 9954 - 9962
(2008/09/18)

Direct, easy, and scalable preparation of (diacetoxyiodo)arenes from arenes using potassium peroxodisulfate as the oxidant
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
p. 7889 - 7891
(2007/10/03)

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
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
p. 190 - 194
(2007/10/03)

Application of [hydroxy(tosyloxy)iodo]benzene in the wittig-ring expansion sequence for the synthesis of β-benzocycloalkenones from α-benzocycloalkenones
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.
p. 217 - 225
(2007/10/03)

Unexpected, drastic effect of triflic acid on oxidative diacetoxylation of iodoarenes by sodium perborate. A facile and efficient one-pot synthesis of (diacetoxyiodo) arenes
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
p. 6984 - 6986
(2007/10/03)

Alternative, easy preparation of (diacetoxyiodo)arenes from iodoarenes using potassium peroxodisulfate as the oxidant
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
p. 1932 - 1934
(2007/10/03)

Straightforward syntheses of hypervalent iodine(III) reagents mediated by selectfluor
(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.
p. 3961 - 3964
(2007/10/03)

New oxidative transformations of alkenes and alkynes under the action of diacetoxyiodobenzene
Treatment of alkenes and alkynes with diacetoxyiodobenzene activated by mineral and organic acids predominantly results in oxidative rearrangement. 1,4-Diphenylbutadiene in MeOH gives 3,4-dimethoxy-1,4-diphenylbut-1-ene.
Yusubov,Zholobova,Filimonova,Chi, Ki-Whan
p. 1735 - 1742
(2007/10/03)

Easy preparation of (diacetoxyiodo)arenes from iodoarenes with sodium percarbonate as the oxidant
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
p. 806 - 809
(2007/10/03)

Syntheses of (diacetoxyiodo)arenes or iodylarenes from iodoarenes, with sodium periodate as the oxidant
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
p. 881 - 891
(2007/10/03)

Formation and synthetic use of oxygen-centred radicals with (diacetoxyiodo)arenes
o-Alkyl- or o-aryl-benzenecarboxylic acids and alcohols containing an aromatic ring are treated with a (diacetoxyiodo)arene-iodine system to give the corresponding cyclized products such as phthalide, benzocoumarin and chromane derivatives in moderate to good yields via the corresponding oxygen-centred radicals. For the carboxylic acids, [bis(trifluoroacetoxy)iodo]benzene functions effectively, while (diacetoxyiodo)benzene is effective for the alcohols. Chromane and its derivatives are obtained as iodinated compounds by hypoiodite species derived from (diacetoxyiodo)benzene and iodine. Copyright 1997 by the Royal Society of Chemistry.
Togo, Hideo,Muraki, Takahito,Hoshina, Yoichiro,Yamaguchi, Kentaro,Yokoyama, Masataka
p. 787 - 793
(2007/10/03)

Oxidation of alkyl and aryl iodides, phenylacetaldehyde and alkenes by dimethyldioxirane. Reaction products and mechanism
Alkyl and aryl iodides are smoothly oxidized to iodosoderivatives and phenylacetaldehyde is oxidized to phenylacetic acid or benzyl acetate by dimethyldioxirane depending on the presence or not of oxygen. These results and the epoxidation or the allylic oxidation of alkenes by the same reagent are explained by a general free-radical mechanism.
Bravo, Anna,Fontana, Francesca,Fronza, Giovanni,Minisci, Francesco,Serri, Anna
p. 6945 - 6948
(2007/10/02)

Reactivity of arenes in substitution and additiopn reactions
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
p. 2135 - 2140
(2007/10/02)

FURTHER FUNCTIONAL GROUP OXIDATIONS USING SODIUM PERBORATE
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
p. 3299 - 3306
(2007/10/02)

GENERAL METHOD FOR SYNTHESIS OF ARYLIODOSYL DERIVATIVES UNDER APROTIC CONDITIONS BY THE REACTION OF IODOSYLBENZENE WITH SUBSTITUTED TRIMETHYLSILANES
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Zefirov, N. S.,Safronov, S. O.,Kaznacheev, A. A.,Zhdankin, V. V.
p. 1633 - 1634
(2007/10/02)

DIRECT IODINATION OF ARYLCYCLOPROPANES
In reaction with phenylcyclopropane in carbon tetrachloride, nitromethane, or chloroform at temperatures between -10 and 20 deg C the complexes of iodine with (bistrifluoroacetoxyiodo)benzene and (diacetoxyiodo)benzene only give the products from the opening of the small ring.By means of the iodine-(diacetoxyiodo)benzene system in the reaction with arylcyclopropanes in a mixture of chloroform and trifluoroacetic acid at -30 deg C it is possible to obtain the products from iodination in the aromatic ring.
Saginova. L. G.,Bondarenko, O. B.,Shabarov, Yu. S.,Gazzaev, R. A.
p. 1935 - 1939
(2007/10/02)

SECONDARY BONDING. PART 13. ARYL-TELLURIUM(IV) AND -IODINE(III) ACETATES AND TRIFLUOROACETATES. THE CRYSTAL AND MOLECULAR STRUCTURES OF BIS-(p-METHOXYPHENYL)TELLURIUM DIACETATE, μ-OXO-BIS HYDRATE, AND BENZENE
The crystal and molecular structures of the title compounds have been determined from diffractometer data by the heavy-atom method, and their preparations are described.Crystals of (p-MeOC6H4)2Te(O2CMe)2 (1) are monoclinic, space group P21/c, with unit-cell dimensions a = 9.529(2), b = 11.984(2), c = 17.035(2) Angstroem, β = 101.70(2) deg, Z = 4, and for 3033 observed reflections (I/?(I) > 3.0), R = 0.022.Crystals of 2O >2*H2O (2) are triclinic, space group , with unit-cell dimensions a = 13.988(3), b= 14.287(3), c = 15.689(3) Angstroem, α = 80.40(2), β = 81.89(2), γ = 86.65(2) deg, Z = 2, and for 5290 observed reflections, R = 0.042.Crystals of PhI(O2CCF3)2 (3) are triclinic, spacegroup , with unit-cell dimensions a = 9.787(4), b= 9.055(3), c = 7.674(3) Angstroem, α = 91.45(3), β = 99.78(3), γ = 89.21(3) deg, Z = 2, and for 2104 observed reflections, R = 0.037.All three compounds have pseudo-trigonal-bipyramidal primary geometry , and form secondary bonds to give pentagonal planar systems around Te and I, also with linear C-Te...O systems.In the light of these results, previously published tellurium nitrate structures are re-interpreted.
Alcock, Nathaniel W.,Harrison, W. David,Howes, Colin
p. 1709 - 1716
(2007/10/02)

Oxidation of Hydrocarbons: Kinetics and Mechanism of Oxidation of substituted by Toluenes Phenyliodosoacetate
Kinetics of Ru(III)chloride catalysed oxidation of toluene and substituted toluenes by phenyliodosoacetate (PIA) in aqueous acetic acid medium at constant acidity are reported.It follows the rate law: V = Kk.The reactions are first order with respect to substrate, zero order with respect to oxidant and first order with respect to catalyst Ru(III).The reactions are found to be largely insensitive to added perchloric acid and acetate ions.The effects of solvent composition and neutral salts have been investigated.The reaction constant φ has been found to be -1,9 pointing to a ionic pathway.Activation parameters have been computed and a suitable mechanism is postulated taking into consideration all the observations.
Pati, Subas C.,Dev., B. R.
p. 176 - 188
(2007/10/02)