Categories: C-O Bond Formation >
Synthesis of Peroxides
Name Reactions
Recent Literature
Eosin Y catalyzes a highly efficient benzylic hydroperoxidation using an energy-economical light source (blue LED), and
a sustainable oxidant (molecular oxygen). Primary, secondary, and tertiary
hydroperoxides as well as silyl, benzyl, and acyl peroxides were successfully
prepared with good yields and excellent functional group compatibility.
J. Inoa, M. Patel, G. Dominici, R. Eldabagh, A. Patel, J. Lee, Y. Xing, J. Org. Chem., 2020, 85,
6181-6187.
Indium(0) mediates an efficient synthesis of benzylic hydroperoxides in very
good yields from a broad range of benzyl bromides under aerobic conditions at
room temperature. In addition, a tandem hydroperoxidation-Michael addition of (E)-1-(bromomethyl)-2-(2-nitrovinyl)benzene
was also demonstrated.
Y. Hou, J. Hu, R. Xu, S. Pan, X. Zeng, G. Zhong,
Org. Lett., 2019, 21, 4428-4432.
An efficient and practical approach to prepare phenols from benzoic acids
using simple organic reagents at room temperature is compatible with various
functional groups and heterocycles and can be easily scaled up. Mechanistic
investigations suggest that the key migration step involves a free carbocation
instead of a radical intermediate.
W. Xiong, Q. Shi, W. H. Liu, J. Am. Chem. Soc.,
2022, 144, 15894-15902.
Iodine catalyzes an environment-friendly and efficient dioxygenation of aryl
alkenes for the construction of vicinal diols in water as solvent with tert-butylhydroperoxide
(TBHP) as the oxidant. The protocol is efficient, sustainable, and operationally
simple. In addition, bisperoxides could be obtained in good yields with Na2CO3
as additive and propylene carbonate as solvent.
X. Gao, J. Lin, L. Zhang, X. Luo, G. Guo, N. Peng, H. Xu, Y. Liu, J. Org. Chem., 2021, 86,
15469-15480.
TBAI catalyzes an efficient, mild, and regioselective synthesis of
4-aryl/alkyl-1-peroxy-but-3-en-2-ols in good yields from
1-substituted-1,3-butadienes in the presence of hydroperoxides and water. This
regioselective orthogonal dioxygenation of a diene can be executed in a simple
operation and tolerates a wide range of substrates.
A. Kumar, G. N. Khatun, R. A. Fernandes, Org. Lett., 2023, 25,
4313-4317.
With an easily accessible cinchona alkaloid catalyst, efficient enantioselective
peroxidation and epoxidation have been successfully developed. Employing readily
available α,β-unsaturated ketones and hydroperoxides, this novel reaction will
open new possibilities in the asymmetric synthesis of chiral peroxides and
epoxides.
X. Lu, Y. Liu, B. Sun, B. Cindric, L. Deng, J. Am. Chem. Soc., 2008,
130, 8134-8135.
A highly enantioselective organocatalytic peroxidation of enals enabled an
enantioselective route toward the core structure of interesting anticancer
natural products including a cyclization cascade of a chiral
bis(epoxy)hydroperoxide and should be applicable to the enantioselective
synthesis of a broad range of chiral 1,2-dioxolanes and 1,2-dioxanes.
L. Hu, X. Lu, L. Deng, J. Am. Chem. Soc., 2015,
137, 8400-8403.
tert-Butylperoxyamido acetals can be generated in high yields under
mild conditions via oxidative functionalization of C-H bonds adjacent to the amide nitrogen atom. Treatment with Grignard reagents enables the synthesis of
α-substituted amides.
H. Yu, J. Shen, Org. Lett., 2014,
16, 3204-3207.
Ketones, ketals, and epoxides can be converted to the corresponding
hydroperoxides in high yields and with high chemoselectivity by reaction with
ethereal H2O2 in the presence of a catalytic amount of MoO2(acac)2.
X. An, Q. Zha, Y. Wu, Org. Lett., 2019, 21,
1542-1546.
Ketones or ketals were readily converted into the corresponding gem-dihydroperoxides
in high yields by treatment with ethereal H2O2 at ambient
temperature in the presence of phosphomolybdic acid (PMA) as catalyst.
Y. Li, H.-D. Hao, Q. Zhang, Y. Wu, Org. Lett., 2009,
11, 1615-1618.
A cobalt-catalyzed peroxidation of silyl enol ethers with molecular oxygen and
triethylsilane provides silyl monoperoxyketals in good yield. These compounds
serve as precursors to peroxycarbenium ions, which undergo annulations to
provide 1,2-dioxolanes.
B. Hurlocker, M. R. Miner, K. A. Woerpel, Org. Lett.,
2014,
16, 4280-4283.
A cobalt-catalyzed peroxidation of silyl enol ethers with molecular oxygen and
triethylsilane provides silyl monoperoxyketals in good yield. These compounds
serve as precursors to peroxycarbenium ions, which undergo annulations to
provide 1,2-dioxolanes.
B. Hurlocker, M. R. Miner, K. A. Woerpel, Org. Lett.,
2014,
16, 4280-4283.
Diacyl peroxides, generated in situ from aliphatic acids and H2O2,
serve as a source for alkyl radicals and also an initiator for the generation of
phosphorus radicals from H-P(O) compounds. A subsequent CuI-catalyzed
cross-coupling of alkyl- and phosphorus-centered radicals provides alkylated
phosphorous compounds in good yields.
C.-K. Li, Z.-K. Tao, A. Shoberu, W. Zhang, J.-P. Zou, Org. Lett.,
2022, 24, 6083-6087.
Commercial, inexpensive 5-mm milliwatt light-emitting diodes are effective
sources for batch microphotochemical oxidations using limited quantities of
singlet oxygen. These atom economical oxidations are useful for labeling
experiments with rare isotopes.
J. M. Carney, R. J. Hammer, M. Hulce, C. M. Lomas, D. Miyashiro, Synlett, 2012, 23,
2560-2566.
Among various rhenium catalysts, Re2O7 in CH3CN
is a remarkably efficient and mild catalyst for the peroxyacetalization of
ketones, aldehydes, or acetals by H2O2 to generate
1,1-dihydroperoxides.
P. Ghorai, P. H. Dussault, Org. Lett.,
2008,
10, 4577-4579.
Ketones reacted with hydrogen peroxide in the presence of iodine to yield gem-dihydroperoxides
in acetonitrile and hydroperoxyketals in methanol in good yields. Aromatic
aldehydes were also converted to gem-dihydroperoxides in acetonitrile and
to hydroperoxyacetals in methanol.
K. Žmitek, M. Zupan, S. Stavber, J. Iskra, J. Org. Chem., 2007,
72, 6534-6540.
Substituted oxiranes were readily transformed to the corresponding
β-hydroxyhydroperoxides in good yields in ethereal H2O2
system with SnCl4 as a catalyst. Alternatively, the use of a
stoichiometric amount of SnCl4 leads to a rearrangement of the
oxiranes to aldehydes. A subsequent addition of ethereal H2O2
solution achieves primary gem-dihydroperoxides in moderate yields.
X. Yan, C. Qiao, Z. Guo, Synlett, 2013, 24, 502-506.
In the presence of catalytic amounts of
phosphomolybdic acid (PMA), ethereal hydrogen peroxide reacted readily with a
range of epoxides at ambient temperature, giving corresponding β-hydroxyhydroperoxides
in good yields.
Y. Li, H.-D. Hao, Y. Wu, Org. Lett., 2009,
11, 2691-2694.
Re2O7 is a mild and efficient catalyst for the
high-yielding condensation of 1,1-dihydroperoxides with ketones or aldehydes to
form 1,2,4,5-tetraoxanes. When applied in tandem with a Re(VII)-catalyzed
synthesis of 1,1-dihydroperoxides, the reaction provides a high-yielding one-pot
conversion of ketones or aldehydes to tetraoxanes.
P. Ghorai, P. H. Dussault, Org. Lett., 2009,
11, 213-216.
P. Ghorai, P. H. Dussault, Org. Lett., 2009,
11, 213-216.
Ketones or ketals were readily converted into the corresponding gem-dihydroperoxides
in high yields by treatment with ethereal H2O2 at ambient
temperature in the presence of phosphomolybdic acid (PMA) as catalyst.
Y. Li, H.-D. Hao, Q. Zhang, Y. Wu, Org. Lett., 2009,
11, 1615-1618.
The acid-catalyzed reaction of β,δ-triketones with hydrogen peroxide produces
tricyclic peroxides selectively in good yields via the monoperoxidation of the
carbonyl groups in β-position and the transformation of the δ-carbonyl group
into an acetal. The resulting peroxides can be easily isolated from the reaction
mixture.
A. O. Terent'ev, I. A. Yaremenko, V. V. Chernyshev, V. M. Dembitsky, G. I.
Nikishin, J. Org. Chem., 2012,
77, 1833-1842.