Oxone, Potassium peroxomonosulfate
The composition of the oxidizing agent Oxone® is 2KHSO5.KHSO4.K2SO4. The active component potassium monopersulfate (KHSO5, potassium peroxomonosulfate) is a salt from the Caro´s acid H2SO5.
The use of Oxone has increased rapidly. Reasons for this are the stability, the simple handling, the non-toxic nature, the versatility of the reagent and the low costs.
B. R. Travis, M. Sivakumar, G. O. Hollist, B. Borhan, Org. Lett., 2003, 5, 1031-1034. DOI
As long as Oxone is stored under dry and cool conditions, it loses about 1% activity per month under release of oxygen and heat. Decomposition to SO2 and SO3 takes place under the influence of heat (starting at 300°C).
Acidic, aqueous solutions of the pure reagent in distilled water are relatively stable. The stability reaches a minimum at pH 9, where the mono anion (HSO5-) has the same concentration as the dianion (SO52-). Iron, cobalt, nickel, copper, manganese and further transition metals can catalyze the decay of Oxone in solution.
The following secondary reactions should be avoided: Halides can be oxidized to halogens (e.g. chloride to chlorine), cyanides react with Oxone under release of hydrogen cyanide, "heavy" transition metals (Cu, Mn, Co, Ni) and their salts lead to the decomposition of Oxone under release of oxygen.
Name Reactions
Recent Literature
Highly efficient, mild, and simple protocols allow the oxidation of aldehydes to
carboxylic acids and esters utilizing Oxone as the sole oxidant. These reactions
may prove to be valuable alternatives to traditional metal-mediated oxidations.
B. R. Travis, M. Sivakumar, G. O. Hollist, B. Borhan, Org. Lett.,
2003, 5, 1031-1034.
B. R. Travis, M. Sivakumar, G. O. Hollist, B. Borhan, Org. Lett.,
2003, 5, 1031-1034.
2-Iodoxybenzenesulfonic acid, which can be generated in situ from
2-iodobenzenesulfonic acid sodium salt, is a much more active catalyst than
modified IBXs for the oxidation of alcohols with Oxone. Highly efficient and
selective methods for the oxidation of alcohols to carbonyl compounds such as
aldehydes, carboxylic acids, and ketones were established.
M. Uyanik, M. Akakura, K. Ishihara, J. Am. Chem. Soc., 2009,
131, 251-262.
M. Uyanik, M. Akakura, K. Ishihara, J. Am. Chem. Soc., 2008,
131, 251-262.
A novel, metal-free oxidation system for the catalytic synthesis of aldehydes
and ketones using TEMPO and a quarternary ammonium salt as catalysts and Oxone
as oxidant proved especially successful for the synthesis of ketones. The mild
conditions tolerate even sensitive silyl protective groups which can otherwise
be cleaved in the presence of Oxone.
C. Bolm, A. S. Magnus, J. P. Hildebrand, Org. Lett., 2000,
2, 1173-1175.
C. Bolm, A. S. Magnus, J. P. Hildebrand, Org. Lett., 2000,
2, 1173-1175.
Catalytic use of o-iodoxybenzoic acid (IBX) in the presence of Oxone
as a co-oxidant is demonstrated for the oxidation of primary and secondary
alcohols. In addition, the in situ oxidation of 2-iodosobenzoic acid (IBA)
and even commercially available 2-iodobenzoic acid (2IBAcid) by Oxone to IBX
allows the use of these less hazardous reagents, in place of potentially
explosive IBX, as catalytic oxidants.
A. P. Thottumkara, M. S. Bowsher, T. K. Vinod, Org. Lett., 2005,
7, 2933-2936.
A. P. Thottumkara, M. S. Bowsher, T. K. Vinod, Org. Lett., 2005,
7, 2933-2936.
Formation of a bromo radical through the oxidation of bromide under mild
conditions enables an oxidative debenzylation of N-benzyl amides and O-benzyl
ethers to provide the corresponding amides and carbonyl compounds in high yields.
K. Moriyama, Y. Nakamura, H. Togo, Org. Lett., 2014,
16, 3812-3815.
The presence of KBr enabled a direct benzylic oxidation of alkylarenes via C-H
bond abstraction using oxone as oxidant under mild conditions. This reaction
proceeded with excellent selectivity by thermal oxidation or photooxidation to
provide a broad range of aryl ketones in high yields.
K. Moriyama, M. Takemura, H. Togo, Org. Lett., 2012,
14, 2414-2417.
Oxidation of alkyl aryl ketones in the presence of Oxone, trifluoroacetic anhydride
and a catalytic amount of iodobenzene affords α-hydroxyalkyl aryl
ketones in good yield. This method provides an effective and economical entry
for the α-hydroxylation of ketones.
C. Chen, X. Feng, G. Zhang, Q. Zhao, G. Huang, Synthesis, 2008,
3205-3208.
In the presence of Oxone as a cheap, stable, and nonhazardous oxidizing reagent,
α,β-unsaturated ketones of defined stereochemistry are transformed into their
corresponding vinyl acetates through a Baeyer-Villiger oxidation. This reaction
tolerates a wide range of functional groups.
B. Poladura, A. Martínez-Castañeda, H. Rodríguez-Solla, R. Llavona, C. Concellón,
V. del Amo, Org. Lett., 2013,
15, 2810-2813.
Oxidative cleavage of various olefins to the corresponding ketones/carboxylic
acids occurs with catalytic amounts of 3,4,5,6-tetramethyl-2-iodobenzoic acid (TetMe-IA)
and oxone as terminal oxidant in acetonitrile-water mixture at rt. The reaction
mechanism involves dihydroxylation of the olefin with oxone, oxidative cleavage
by TetMe-IBX, and oxidation of the aldehyde functionality to the corresponding
acid with oxone.
J. N. Moorthy, K. N. Parida, J. Org. Chem.,
2014,
79, 11431-11439.
Specific oxidation protocols have been developed for the cleavage of styrenes,
aliphatic olefins, and terminal aliphatic olefins to carbonyl compounds with
ruthenium trichloride as catalyst. Olefins that are not fully substituted are
converted to aldehydes rather than carboxylic acids.
D. Yang, C. Zhang, J. Org. Chem., 2001, 66,
4814-4818.
The OsO4-catalyzed direct oxidation of olefins via the
carbon-carbon cleavage of an osmate ester by the action of oxone allows the
preparation of ketones or carboxylic acids in high yields. This method
should be applicable as an alternative to ozonolysis.
B. R. Travis, R. S. Narayan, B. Borhan, J. Am. Chem. Soc., 2002,
124, 3824-3825.
The OsO4-catalyzed direct oxidation of olefins via the
carbon-carbon cleavage of an osmate ester by the action of oxone allows the
preparation of ketones or carboxylic acids in high yields. This method
should be applicable as an alternative to ozonolysis.
B. R. Travis, R. S. Narayan, B. Borhan, J. Am. Chem. Soc., 2002,
124, 3824-3825.
Oxone oxidatively degrades 1,3-dicarbonyl compounds and α-hydroxy ketones to
carboxylic acids. This method compliments existing methodologies and is in
general a milder alternative to the haloform reaction.
S. W. Ashford, K. C. Grega, J. Org. Chem., 2001,
66, 1523-1524.
An ambient electro-oxidation of arylacetylenes proceeds smoothly at certain
applied potentials in a mixed solution of acetonitrile and water with potassium
peroxymonosulfate to provide aryl carboxylic acids in good yields. This
environmentally friendly synthesis exhibits excellent functional-group tolerance and
does not require transition metal catalysts, extra acids/bases, and high
temperature.
H. Yuan, M. Sun, T. Zhang, G. Wu, Y. Zhang, Synthesis, 2024,
56, 179-186.
A new mild RuO4-catalyzed ketohydroxylation of olefins is
reported. α-Hydroxy ketones were obtained with high regioselectivity and
in good to excellent yields.
B. Plietker, J. Org. Chem., 2003,
68, 7123-7125.
A biologically inspired cis-dihydroxylation of a wide range of olefins
using inexpensive and readily available mononuclear non-heme manganese complexes
bearing tetradentate nitrogen-donor ligands and aqueous hydrogen peroxide (H2O2)
and potassium peroxymonosulfate (KHSO5) as terminal oxidants provides
cis-diols in practically useful yields and enantioselectivity.
J. Chen, J. Zhang, Y. Sun, Y. Xu, Y. Yang, Y.-M. Lee, W. Ji, B. Wang, W. Nam,
B. Wang, J. Am. Chem. Soc.,
2023, 145, 27626-27638.
The use of Oxone/aluminum trichloride mixture enables an α,α-dichlorination
of β-keto esters and 1,3-diketones in aqueous medium. The dichlorinated
compounds have been produced in one step, high yields, and short reaction times.
V. Giannopoulos, N. Katsoulakis, I. Smonou, Synthesis, 2022, 54,
2457-2463.
pecific oxidation protocols have been developed for the cleavage of styrenes,
aliphatic olefins, and terminal aliphatic olefins to carbonyl compounds with
ruthenium trichloride as catalyst. Olefins that are not fully substituted are
converted to aldehydes rather than carboxylic acids.
D. Yang, C. Zhang, J. Org. Chem., 2001, 66,
4814-4818.
Transformation of epoxides to β-alkoxy alcohols, acetonides, and α-alkoxy
ketones is achieved by using molybdenum(VI) dichloride dioxide (MoO2Cl2)
as a catalyst. Alcohol, aldehyde, oxime, tosyl, and tert-butyldimethylsilyl
functional groups are tolerated during the methanolysis and acetonidation of the
functionalized epoxides.
K. Jeyakumar, D. K. Chand, Synthesis, 2008,
807-819.
A mild and convenient oxidative Nef reaction using Oxone is described.
Following this procedure primary and secondary nitroalkanes generates
carboxylic acids and ketones, respectively, both in good yields.
P. Ceccherelli, M. Curini, M. C. Marcotullino, F. Epifano, O. Rosati, Synth. Commun., 1998, 28, 3057-3064.
α-Keto esters can be prepared via Mannich addition of ethyl diazoacetate to
imines followed by oxidation of the diazo group with Oxone. Implementation of a
recently developed dynamic kinetic resolution of β-substituted-α-keto esters via
Ru(II)-catalyzed asymmetric transfer hydrogenation provides enantioenriched
anti-α-hydroxy-β-amino acid derivatives in high diastereo- and
enantioselectivity.
C. G. Goodman, D. T. Do, J. S. Johnson, Org. Lett., 2013,
15, 2446-2449.
An oxidative Strecker reaction of aldehydes, amines, and TMSCN in a biphasic
solvent system in the presence of Oxone, TBAB and sodium bicarbonate affords
α-iminonitriles in good yields. This three component reaction is applicable to a
wide range of aldehydes and amines.
J.-B. Gualtierotti, X. Schumacher, Q. Wang, J. Zhu, Synthesis, 2013, 45,
1380-1386.
The use of Oxone allows the conversion of various aryl-, heteroaryl-, alkenyl-,
and alkyltrifluoroborates into the corresponding oxidized products in excellent
yields. This method tolerates a broad range of functional groups, and in
secondary alkyl substrates it was demonstrated to be completely stereospecific.
G. A. Molander, L. N. Cavalcanti, J. Org. Chem., 2011,
76, 623-630.
G. A. Molander, L. N. Cavalcanti, J. Org. Chem., 2011,
76, 623-630.
A two-step sequence of asymmetric dihydroxylation and regioselective
monooxidation gave enantiopure α-hydroxy ketones (acyloins). The
combination of RuCl3/Oxone/NaHCO3 was used in the
first catalytic regioselective oxidation of vic-diols to
α-ketols.
B. Plietker, Org. Lett., 2004, 6, 289-291.
An efficient method for the oxidative cleavage of internal and terminal
alkynes to carboxylic acids using a combination of RuO2/Oxone/NaHCO3
in a CH3CN/H2O/EtOAc solvent system is described.
Various alkynes, regardless of their electron density, were oxidized to
carboxylic acids in excellent yield.
D. Yang, F. Chen, Z.-M. Dong, D.-W. Zhang, J. Org. Chem., 2004, 69, 209-212.
A mixture of Oxone and trifluoroacetic acid enables a simple and mild metal-free
oxidation of various ketones or arylalkynes to the corresponding carboxylic
acids in excellent yields.
K. A. A. Kumar, V. Venkateswarlu, R. A. Vishwakarma, S. D. Sawant,
Synthesis, 2015, 47, 3161-3168
A highly efficient, rapid and regioselective protocol for the ring bromination
of aromatic compounds under mild conditions can be conducted with ammonium
bromide as a source of bromine source and Oxone as an oxidant. Various aromatic
compounds reacted smoothly to give the corresponding monobrominated products in
good yields in very short reaction times.
N. Naresh, M. A. Kumar, M. M. Reddy, P. Swamy, J. B. Nanubolu, N. Narender, Synthesis, 2013, 45,
1497-1504.
A simple, efficient and mild method for the selective bromination of
activated aromatic compounds using ammonium bromide as the source of bromine and
Oxone as the oxidant in methanol or water as solvent proceeds at ambient temperature in good yields without a catalyst.
M. A. Kumar, C. N. Rohitha, S. J. Kulkarni, N. Narender, Synthesis, 2010,
1629-1632.
Hofmann rearrangement of carboxamides to carbamates using Oxone as an oxidant
can be efficiently catalyzed by iodobenzene via hypervalent iodine species
generated in situ in the presence of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) in
aqueous methanol solutions. Under these conditions, Hofmann rearrangement of
various carboxamides affords corresponding carbamates in high yields.
A. Yoshimura, K. R. Middleton, M. W. Luedtke, C. Zhu, V. V. Zhdankin, J. Org. Chem., 2012,
77, 11399-11404.
Alkylcarboxamides can be converted to the respective alkylcarbamates by
Hofmann rearrangement using hypervalent iodine species generated in situ from
PhI and Oxone in methanol. In addition, substituted benzamides can be converted
to the respective quinone derivatives by treatment with Oxone and iodobenzene in
aqueous acetonitrile.
A. A. Zagulyaeva, C. T. Banek, M. S. Yusubov, V. V. Zhdankin, Org. Lett., 2010,
12, 4644-4647.
Visible-light-driven oxidations of various N-alkylamides proceed
efficiently under mild conditions to provide imines by using Oxone as the
oxidant in the presence of a catalytic amount of KBr in H2O/CH2Cl2
under irradiation by an 8 W white LED at room temperature. Experimental studies
suggest that an imine, obtained from the substrate amide via a radical process,
is the key intermediate.
C. Mei, Y. Hu, W. Lu, Synthesis, 2018, 50,
2999-3005.
Grubbs' 2nd generation metathesis catalyst can be used in tandem olefin
metathesis/oxidation protocols. These ruthenium-catalyzed processes provide
access to cis-diols or α-hydroxy ketones from simple olefinic starting
materials.
A. A. Scholte, M. H. An, M. L. Snapper, Org. Lett., 2006, 8, 4759-4762.
A general, efficient and metal-free protocol for the direct oxidation of
secondary amines to nitrones tolerates other functional groups or existing
stereogenic centers using Oxone in a biphasic basic medium as the sole oxidant.
C. Gella, È. Ferrer, R. Alibés, F. Busqué, P. de March, M. Figueredo, J. Font, J. Org. Chem., 2009,
74, 6365-6367.
An efficient one-pot multistep strategy comprising auto-oxidative
difunctionalization of alkenes, oxidation of sulfides, and a further reduction
of peroxides enables the synthesis of complex β-hydroxysulfone derivatives from
thiophenols and alkenes. This method offers readily available substrates,
low-cost and environmental benign reagents, nontoxic and renewable solvents, and
mild reaction conditions.
Y. Wang, W. Jiang, C. Huo, J. Org. Chem.,
2017, 82, 10628-10634.
Cyclic ketones were quickly and quantitatively converted to 5-, 6-, and
7-membered lactones by treatment with Oxone, a cheap, stable, and nonpollutant
oxidizing reagent in 1 M NaH2PO4/Na2HPO4
water solution (pH 7). These simple and green conditions avoid the formation of
hydroxyacid. With some changes, the method can also be applied to
water-insoluble ketones.
V. Bertolini, R. Appiani, M. Pallavicini, C. Bolchi, J. Org. Chem., 2021, 86,
15712-15716.
[4-Iodo-3-(isopropylcarbamoyl)phenoxy]acetic acid is a highly reactive and
easily separable catalyst for the oxidative cleavage of
tetrahydrofuran-2-methanols to γ-lactones in the presence of Oxone as the
terminal oxidant.The catalyst and product were easily separated by only
liquid-liquid separation without chromatography.
T. Yakura, T. Fujiwara, H. Nishi, Y. Nishimura, H. Nambu, Synlett, 2018, 29,
2316-2320.
A convenient, safe, and green protocol, that uses oxone/halide and Fenton
bromide, achieves a halogenative semipinacol rearrangement at room temperature.
The key feature of this method is the green in situ generation of reactive
halogenating species from oxidation of halide with oxone or H2O2,
which produces a nontoxic byproduct (potassium sulfate or water).
L. Song, Y. Zhou, H. Liang, H. Li, Y. Lai, H. Yao, R. Lin, R. Tong, J. Org. Chem., 2023, 88,
504-512.
Iodocyclization of unsaturated tosylamides promoted by Oxone oxidation of KI
afforded, in good yields, N-tosyl iodopyrrolidines and piperidines.
M. C. Marcotullio, V. Campagna, S. Sternativo, F. Costantino, M. Curini,
Synthesis, 2006, 2760-2766.
The oxidative intramolecular bromo-amination of various N-alkenyl
sulfonamides and N-alkenoxyl sulfonamides via umpolung of alkali metal
bromides occurred exo-selectively to generate pyrrolidines and isoxazolidines
in high yields with good diastereoselectivities. This method provided the
desired products with a low amount of organic waste.
K. Moriyama, Y. Izumisawa, H. Togo, J. Org. Chem., 2011,
76, 7249-7255.
A hypervalent iodine species, which is formed in situ in the presence of oxone
as terminal oxidant, catalyzes the oxidation of aldoximes to generate nitrile
oxides. A subsequent reaction with alkenes gives the corresponding isoxazolines
in good yields, whereas the reaction with alkynes gives the corresponding
isoxazoles in moderate yields.
A. Yoshimura, K. R. Middleton, A. D. Todora, B. J. Kastern, S. R. Koski, A. V.
Maskaev, V. V. Zhdankin, Org. Lett., 2013,
15, 4010-4013.
Addition of oxone to a mixture of a 1,2-phenylenediamine and an
aldehyde in wet DMF results in rapid formation of benzimidazoles under very mild
conditions. Products are isolated in high purity in most cases by simple aqueous
precipitation. The reaction is applicable to a wide range of substrates but does
not allow the conversion of aldehydes that are sensitive to oxone under acidic
reaction conditions.
P. L. Beaulieu, B. Haché, E. von Moos, Synthesis, 2003, 1683-1692.
An oxone mediated tandem transformation of 2-aminobenzylamines to 2-substituted
benzimidazoles occurs at room temperature with aromatic, heteroaromatic, and
aliphatic aldehydes. Initial condensation of 2-aminobenzylamine with appropriate
aldehydes afforded a tetrahydroquinazoline intermediate which underwent
oxone-mediated ring distortion to afford the desired compounds in good yields.
S. Hati, P. K. Dutta, S. Dutta, P. Munshi, S. Sen, Org. Lett.,
2016, 18, 3090-3093.
An electron-withdrawing group on the nitrogen of indoles enables a mild C2
chlorination and bromination with stoichiometric halide and oxone, while C3
halogenation could be selectively achieved by using stoichiometric halide
without dependence on the electronic property of the protecting group on the
indole nitrogen.
T. Zheng, J. Xu, S. Cheng, J. Ye, S. Ma, R. Tong, J. Org. Chem., 2023, 88,
11497-11503.
An electron-withdrawing group on the nitrogen of indoles enables a mild C2
chlorination and bromination with stoichiometric halide and oxone, while C3
halogenation could be selectively achieved by using stoichiometric halide
without dependence on the electronic property of the protecting group on the
indole nitrogen.
T. Zheng, J. Xu, S. Cheng, J. Ye, S. Ma, R. Tong, J. Org. Chem., 2023, 88,
11497-11503.
A Cu(II)-catalyzed acylation of acyloins with a thiol ester present in Wittig
reagents under neutral conditions through a push-pull mechanism enables a
one-pot lactonization to yield butenolides. The synthetic utility of this method
for the synthesis of natural products is shown.
K. Matuso, M. Shindo, Org. Lett., 2010,
12, 5346-5349.
α-Bromo- or α-chloro-α,β-unsaturated carbonyl compounds were prepared in good
yields by addition of hydrobromic acid or hydrochloric acid to α,β-unsaturated
carbonyl compounds in the presence of Oxone in CH2Cl2
followed by treatment of the resulting dihalides with Et3N.
K.-M. Kim, I.-H. Park, Synthesis,
2004, 2641-2644.
The use of oxone in trifluoroacetic acid enables a general and convenient
synthesis of [bis(trifluoroacetoxy)iodo]arenes at room temperature. The
oxidation of perfluoroalkyl iodides gives [bis(trifluoroacetoxy)iodo]perfluoroalkanes,
that can be converted to stable [hydroxy(tosyloxy)iodo]perfluoroalkanes.
A. A. Zagulyaeva, M. S. Yusubov, V. V. Zhdankin, J. Org. Chem., 2010,
75, 2119-2122.
The use of iodine and Oxone in acetic acid/acetic anhydride enables an
inexpensive, environmentally friendly, and highly efficient regio- and
diastereoselective iodoacetoxylation of alkenes and alkynes in a simple one-pot
process.
T. Hokamp, A. T. Storm, M. Yusubov, T. Wirth,
Synlett, 2018, 29, 415-418.
An oxidative desulfurization approach enables the construction of oxadiazole and
thiadiazole heterocycles in the presence of iodobenzene and Oxone. The use of
iodobenzene and the inexpensive readily available oxidant Oxone makes the
reaction system simple and versatile for desulfurization.
K. N. Patel, N. C. Jadhav, P. B. Jagadhane, V. N. Telvekar, Synlett, 2012, 23,
1970-1972.
A ruthenium catalyzed intramolecular C-S coupling reaction of N-arylthioureas
enables the synthesis of 2-aminobenzothiazoles via an electrophilic ruthenation
pathway instead of a direct C-H activation. In case of meta-substituents
on the N-arylthiourea, stereoelectronic effects dictate the final
regioselective outcome of the reaction.
S. Sharma, R. S. Pathare, A. K. Maurya, K. Gopal, T. K. Roy, D. M. Sawant, R. T.
Pardasani, Org. Lett., 2016, 18,
356-359.
