536-80-1

Usage

Uses

Used in Organic Synthesis:
Iodosobenzene is used as an oxygen transfer reagent for stoichiometric or catalytic cross-functionalization of alkenes, alcohols, sulfides, and organometallic compounds. It serves as an oxidizing and acetoxylating agent in organic synthesis and is actively involved in the preparation of (Z)-3,7-dimethyl-2,6-octadien-1-al (neral) from (Z)-3,7-dimethyl-2,6-octadien-1-ol (nerol) in the presence of 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO). It is a useful reagent for the synthesis of a wide variety of heterocyclic compounds and is also used in the Pd-catalyzed 2-arylation of indoles.
Used in Organic Sulfur Compounds:
Iodosobenzene is a relatively new, selective oxidizing agent that is particularly useful for the preparation of sulfoxides from unsaturated or otherwise sensitive sulfides. The preparation of diallyl, di-2-hydroxyethyl, and phenyl 2-chloroethyl sulfoxides illustrates its use. Iodosobenzene diacetate behaves similarly and oxidizes diphenyl and 4-nitro-phenyl 4'-carboxyphenyl sulfide exclusively to the sulfoxides. However, this reagent failed to oxidize bis(2-nitro-4-trifluoromethylphenyl) sulfide and, in the case of bis(2-aminophenyl) sulfide, it gave complex products. Iodosobenzene diacetate caused diacetoxylation of the heterocycle of 2,5-diphenyl-1,4-dithiadiene rather than oxidation of the sulfide function, and with 2,5-diphenyl-1,4-dithiadiene-1-oxide, unexpected results were obtained.

Synthesis

Iodosobenzene has been prepared by the action of sodium or potassium hydroxide solution on iodobenzene dichloride and by addition of water to the dichloride.Iodosobenzene is prepared from iodobenzene.It is prepared by first oxidizing iodobenzene by peracetic acid. Hydrolysis of resulting diacetate affords "PhIO":C6H5I + CH3CO3H + CH3CO2H → C6H5I(O2CCH3)2 + H2OC6H5I(O2CCH3)2 + H2O → C6H5IO + 2CH3CO2Hhttp://orgsyn.org

InChI:InChI=1/C6H5IO/c8-7-6-4-2-1-3-5-6/h1-5H

Upstream product

• 591-50-4 iodobenzene 
• 932-72-9 (Dichloroiodo)benzene 
• 3240-34-4 [bis(acetoxy)iodo]benzene 
• 696-33-3 iodoxybenzene 
• 123-30-8 4-amino-phenol 
• 10028-15-6 ozone 
• 7601-90-3 perchloric acid 
• 64-19-7 acetic acid 
• 7664-93-9 sulfuric acid 
• 7732-18-5 water 
• 26735-53-5 iodobenzene difluoride 
• 429-41-4 tetrabutyl ammonium fluoride 
• 1613-37-2 Quinoline N-oxide 
• 16975-78-3 bis(acetoxy)iodylbenzene 

Downstream Products

• 29393-26-8 phenyl-[2]thienyl-iodonium ; chloride 
• 54527-51-4 [bis-(2,2-dichloroacetyloxy)iodo]benzene 
• 2217-78-9 diphenyl-iodonium ; hydroxide 
• 53904-18-0 (4-methoxy-phenyl)-phenyl-iodonium ; iodide 
• 2665-61-4 (p-methoxyphenyl)(phenyl)iodonium bromide 
• 98805-82-4 (4-acetylamino-phenyl)-phenyl-iodonium ; iodide 
• 55145-91-0 4-acetylaminodiphenyliodonium bromide 
• 591-50-4 iodobenzene 
• 92-52-4 biphenyl 
• 10182-84-0 diphenyliodonium 
• 2665-60-3 (p-methylphenyl)phenyliodonium bromide 
• 6597-18-8 (dibenzoyloxyiodo)benzene 
• 1932-53-2 1-phenyl-1λ³-[1,2,7]iodadioxepane-3,6-dione 
• 85083-59-6 iodobenzene dimethoxide 

Relevant academic research and scientific papers

Para -Selective C-H bond functionalization of iodobenzenes

Selective C-H bond activation and functionalization is an invaluable and eco-friendly tool for new chemical bond construction. Recently, great progress has been made in the highly selective ortho- and meta-C-H bond functionalization of arene derivatives. In contrast, the remote para-C-H bond functionalization still remains a challenge. Herein, an oxidation-induced strategy for para-selective C-H bond functionalization of iodobenzenes towards the synthesis of various useful asymmetric diaryl ethers was demonstrated. This strategy not only provides a novel method for para-C-H bond functionalization, but also proposes a general idea for the development of new, highly selective para-C-H functionalization reactions.

Chiral-at-Ruthenium Catalyst with Sterically Demanding Furo[3,2-b]pyridine Ligands

A sterically demanding derivative of a previously introduced chiral-at-metal ruthenium(II) catalyst scaffold is introduced. It is composed of two bidentate furo[3,2-b]pyridyl functionalized N-heterocyclic carbene ligands. Their cis-coordination generates helical chirality and a stereogenic ruthenium center. Two additional labile acetonitriles compose the catalytic site which is highly shielded by two 2-(tert-butyl)furo[3,2-b]pyridine moieties. The synthesis of the non-racemic ruthenium catalyst and its catalytic properties for the enantioselective alkynylation of 2,2,2-trifluoroacetophenone and pentafluorobenzaldehyde are reported and compared with sterically less demanding derivatives.

C-N Coupling via Antiaromatic Endocyclic Nitrenium Ions

Herein, we report a C-N coupling reaction via antiaromatic endocyclic nitrenium ions. The nitrenium ion intermediate was generated by a combination of iodine(III) reagent PhI(OCOCF3)2 and the N-H center of benzimidazole units at ambient laboratory conditions. Metal-free synthesis of benzimidazole-fused phenanthridine derivatives was achieved in good to excellent yields.

Modifying the Product Distribution of a Reaction within the Controlled Microenvironment of a Colloidosome

A water-soluble colloidosome composed of PGMA-PS latex was used as a microcapsule to host a catalyzed oxidation reaction within its dodecane core. When compared to a control reaction a significant colloidosome effect was observed. Specifically, a 233% increase in the relative yield of all products was observed for the colloidosome reaction. Furthermore, when the product distributions were calculated it was evident that a switch in selectivity had taken place. These studies showed there is a significant reduction in the relative yield of the epoxide product compared to the remaining oxidation products. Additional control experiments confirmed that rate enhancements were not simply a result of concentration and that reactions were not occurring in the outer latex phase. As a consequence of these control experiments, we suggest that the colloidosome enhancement and shift in product distribution, comes about from differences in electronic environment at or close to the interface between the internal oil phase and the outer colloidal particles. This environment is able to stabilize any specific intermediates and or transition states leading to enhanced reactions for these products and higher relative yields.

N?N Bond Formation Using an Iodonitrene as an Umpolung of Ammonia: Straightforward and Chemoselective Synthesis of Hydrazinium Salts

The formation of hydrazinium salts by N?N bond formation has typically involved the use of hazardous and difficult to handle reagents. Here, mild and operationally simple conditions for the synthesis of hydrazinium salts are reported. Electrophilic nitrogen transfer to the nitrogen atom of tertiary amines is achieved using iodosylbenzene as oxidant and ammonium carbamate as the N-source. The resulting process is highly chemoselective and tolerant to other functional groups. A wide scope is reported, including examples with bioactive molecules. Insights on the structure of hydrazinium salts were provided by X-ray analysis. (Figure presented.).

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.

CO2-activated NaClO-5H2O enabled smooth oxygen transfer to iodoarene: A highly practical synthesis of iodosylarene

A safe, rapid, and environmentally friendly synthesis of iodosylarene (ArIO) has been developed using NaClO under a carbon dioxide (CO2) atmosphere. Exposure of iodoarene to NaClO-5H2O in acetonitrile under CO2 (1 atm) resulted in the clean formation of ArIO within 10 minutes in high yield. The absence of a base in this method enables the direct use of in-situ-generated iodosylarene not only for a variety of oxidative transformations (synthesis of sulfilimine, pentavalent bismuth, benzyne adduct, etc.), but also for the synthesis of iodonium ylide and imino-λ3-iodane in one pot.

Intercepting a transient non-hemic pyridine: N -oxide Fe(iii) species involved in OAT reactions

In the context of bioinspired OAT catalysis, we developed a tetradentate dipyrrinpyridine ligand, a hybrid of hemic and non-hemic models. The catalytic activity of the iron(iii) derivative was investigated in the presence of iodosylbenzene. Unexpectedly, MS, EPR, M?ssbauer, UV-visible and FTIR spectroscopic signatures supported by DFT calculations provide convincing evidence for the involvement of a relevant FeIII-O-NPy active intermediate. This journal is

PhI(OTf)2 Does Not Exist (Yet)**

PhI(OTf)2 has been used for the past 30 years as a strong I(III) oxidant for organic and inorganic transformations. It has been reported to be generated in situ from the reactions of either PhI(OAc)2 or PhI=O with two equivalents of trimethylsilyl trifluoromethanesulfonate (TMS-OTf). In this report it is shown that neither of these reactions generate a solution with spectroscopic data consistent with PhI(OTf)2, with supporting theoretical calculations, and thus this compound should not be invoked as the species acting as the oxidant for transformations that have been associated with its use.

Site-Selective Copper-Catalyzed Azidation of Benzylic C-H Bonds

Site selectivity represents a key challenge for non-directed C-H functionalization, even when the C-H bond is intrinsically reactive. Here, we report a copper-catalyzed method for benzylic C-H azidation of diverse molecules. Experimental and density functional theory studies suggest the benzyl radical reacts with a CuII-azide species via a radical-polar crossover pathway. Comparison of this method with other C-H azidation methods highlights its unique site selectivity, and conversions of the benzyl azide products into amine, triazole, tetrazole, and pyrrole functional groups highlight the broad utility of this method for target molecule synthesis and medicinal chemistry.