Iodosobenzene oxidants

Hydroxy(tosyloxy)iodobenzene 2014 reacts with phenyltrimethylsilane 81 in boiling acetonitrile to give diphenyliodonium tosylate 2015 and trimethylsilanol 4 or HMDSO 7 [184, 185]. Likewise, treatment of 2,5-bis(trimethylsilyl)furan 2016 with 2014 in boiling acetonitrile/methanol affords 78% iodonium tosylate 2017 and trimethylsilanol 4 [185]. In the presence of Bp3-OEt2 iodosobenzene oxidizes allyl-trimethylsilanes such as 2018 to unsaturated aldehydes such as 2019 in 63% yield, with formation of iodobenzene and trimethylsilanol 4 [186]. Analogously, vinyltrimethylsilanes such as (Z)-l-trimethylsilyl-2-phenylethylene 2020 afford, via 2021, acetylenes such as phenylacetylene in 61% yield and iodobenzene and trimethylsilanol 4 [187] (Scheme 12.54). 

The perruthenate procedure (Entry 2) is also based on a general amine to imine oxidation. The iodosobenzene method (Entry 3) is an application of a... 

Low yields of the 5-acetyl-l0,11-epoxy derivative 11 (R = Me) are also obtained by oxidation of 5-acetyl-5//-dibenz[/>,/]azepine (10, R = Me) with iodoxybenzene and vanadium(lll) acetylacetonate, and with iodosobenzene and iron(lll) porphyrin.220... 

Iodosobenzene diacetate is used as a reagent for the preparation of glycol diacetates from olefins,9 for the oxidation of aromatic amines to corresponding azo compounds,10 for the ring acetylation of N-arylacetamides,11 for oxidation of some phenols to phenyl ethers,12 and as a coupling agent in the preparation of iodonium salts.13 Its hydrolysis to iodosobenzene constitutes the best synthesis of that compound.14... 

Iodoxybenzene has been prepared by the disproportionation of iodosobenzene,4Hi by oxidation of iodosobenzene with hypo-chlorous add or bleaching powder,7 and by oxidation of iodobenzene with hypochlorous acid or with sodium hydroxide and bromine.8 Other oxidizing agents used with iodobenzene include air,3 chlorine in pyridine,9 Caro s acid,19-11 concentrated chloric acid,15 and peracetic acid solution.13 Hypochlorite oxidation of iodobenzene dichloride has also been employed.14... 

Peracetic acid, far oxidation of iodo-benzene to iodosobenzene diacetate, 43, 62... 

Triphenylphosphine oxide (and PhsAsO or Ph2SeO) are reduced by MesSiNs 19, via the labile diazidophosphines 1780, to triphenylphosphine (triphenylarsine or diphenylselenide), nitrogen, and HMDSO 7, whereas iodosobenzene gives, via 1781, iodobenzene, nitrogen, and HMDSO 7 [30] (Scheme 12.9). 

Reaction of N,N-dimethylaniline with 1-cyanobenziodoxol 1783 to afford N-methyl-N-cyanomethylaniline 1784 in 97% yield has been discussed in Section 12.1 [31]. Analogously, oxidation of dimethylaniline with iodosobenzene and trimethylsilyl azide 19 at 0°C in CDCI3 gives the azido compound 2040 in 95% yield, iodobenzene, and HMDSO 7 [194, 195] (Scheme 12.56). Likewise, the nucleophilic catalyst 4-dimethylaminopyridine (DMAP) is oxidized, in 95% yield, to the azide 2041, which is too sensitive toward hydrolysis to 4-N-methylaminopyri-dine to enable isolation [194, 195]. Amides such as 2042, in combination with tri-... 

Oxidation of reserpine (109) with iodosobenzene diacetate in alcoholic medium (284) afforded in a single step the corresponding 7-alkoxyindolenine derivatives... 

IODOSOBENZENE, 43, 60 IODOSOBENZENE DIACETATE, 43, 62 hydrolysis to iodosobenzene, 43, 60 4-Iodosobiphenyl, 43, 61 4-Iodosobipbenyl diacetate, 43, 64 o-Iodosophenetole, 43, 61 o-Iodosophenetole diacetate, 43, 64 m-Iodosotoluene, 43, 61 o-Iodosotoluene, 43, 61 -Iodosotoluene, 43,61 jTodosotoluene diacetate, 43, 64 o-Iodosotoluene diacetate, 43, 64 p lodosotoluene diacetate, 43, 64 2-Iodoso-w-xylene, 43, 61 2-Iodoso- -xylene, 43, 61 4-Iodoso-m-xylene, 43, 61 2-Iodoso-wt-xylene diacetate, 43,64 4-Iodoso-m-xylene diacetate, 43,64 2-Iodoso- -xylene diacetate, 43, 64 N-Iodosuccinimide, 42, 73 Iodoxyarenes by oxidation of aryl iodides, 43, 66 IODOXYBENZENE, 43, 65... 

If cyclohexanecarboxaldehyde is incubated with CYP2B4, NADPH, and cytochrome P450 reductase, the aldehyde-cyclohexyl ring carbon-carbon bond is cleaved generating cyclohexene and formic acid (150) (Fig. 4.81). The reaction is supported if hydrogen peroxide replaces NADPH and cytochrome P450 reductase but is not supported if other oxidants at the same oxidation equivalent as peroxide but bypass the peroxy form of P450 such as iodosobenzene, m-chloroperbenzoic acid, or cumyl hydroperoxide are used. These... 

The kinetics of the catalytic oxidation of cyclopentene to glutaraldehyde by aqueous hydrogen peroxide and tungstic acid have been studied and a compatible mechanism was proposed, which proceeds via cyclopentene oxide and /3-hydroxycyclopentenyl hydroperoxide. " Monosubstituted heteropolytungstate-catalysed oxidation of alkenes by t-butyl hydroperoxide, iodosobenzene, and dioxygen have been studied a radical mechanism was proved for the reaction of alkenes with t-BuOOH and O2, but alkene epoxidation by iodosobenzene proceeds via oxidant coordination to the catalyst and has a heterolytic mechanism. ... 

As for chemical paths to cation-radical generation, the following oxidants deserve to be mentioned concentrated (98%) sulfuric acid (Carrington et al. 1959, Hyde and Brown 1962, Carter 1971), persufate (Minisci et al. 1983), iodosobenzene bis(trifluoroacetate) (Alberti et al. 1999), and chlorine dioxide (Handoo et al. 1985, Sokolov et al. 1999). The following metal ions were used in many applications Tl(III) (Elson and Kochi 1973, McKillop and Taylor 1973), Mn(III) (Andrulis... 

Oxidation of dienones with iodosobenzene in the presence of a catalytic amount of tetraphenylporphinatomanganese(III) chloride [TPP(III)C1] affords a mixture of the corresponding oxiranes and 2-pyrones (85CL665) (Eq. 4). 

Another important variant of the preceding approach is the cycloaddition reaction between monocarbonyl iodonium salt 47 and an alkene to give dihydrofuran 48 (88TL3703 89JOC2605). The iodonium salt 47 is generated by the oxidation of acetophenone silyl enol ether (46) with iodosobenzene in the presence of fluoboric acid. 

Coumaran-3-one without substitution at the 2-position can be synthesized by oxidation of silyl enol ether 62 with iodosobenzene under Lewis acid conditions. a-Hydroxyketone 63 is formed as a side product (86SC1239). 

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