Cumene Hydroperoxide (CMHP, CHP)
Cumene hydroperoxide is a relatively stable organic peroxide. This oxidizing agent is commercially available with a purity of ~80%. A 0.2 M solution in benzene has a half-life of 29 hours at 145°C. The decomposition products of cumene hydroperoxide are methylstyrene, acetophenone, and cumyl alcohol. Pure cumene hydroperoxide can be stored at room temperature, but the potential for an uncontrolled reaction and explosion is high. Cumyl as well as other hydroperoxides can undergo rapid decomposition under the influence of a wide range of trace compounds, such as acids and metals. (M. A. Francisco, Chem. Eng. News, 1993, 71, 4. Link).
Recent Literature
A new catalytic system for the asymmetric epoxidation of allylic alcohols
has been developed featuring high enantioselectivity for Z olefins,
catalyst loading of less than 1 mol%, reaction temperatures of 0°C to room
temperature over a shorter time, and simple workup procedures for small
expoxy alcohols.
W. Zhang, A. Basak, Y. Kosugi, Y. Hoshino, H. Yamamoto, Angew. Chem. Int. Ed.,
2005,
44, 4389-4391.
Chiral bishydroxamic acid ligands provided good yields and high
enantioselectivities in the vanadium-catalyzed asymmetric epoxidation of
homoallylic alcohols.
W. Zhang, H. Yamamoto, J. Am. Chem. Soc., 2007,
129, 286-287.
A new and
efficient chiral catalyst system, lanthanum-chiral
BINOL-tris(4-fluorophenyl)phosphine oxide-cumene hydroperoxide, was
developed for the epoxidation of α,β-unsaturated ketones, thus providing
the corresponding epoxy ketones with excellent enantioselectivities (up
to >99% ee) in good to excellent yields at room temperature.
R. Kino, K. Daikai, T. Kawanami, H. Furuno, J. Inanaga, Org. Biomol. Chem., 2004, 2, 1822-1824.
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.
An I2/CHP-mediated cross-coupling reaction of isocyanides with
readily accessible amines gives carbodiimides in good yields. This metal-free
strategy for coupling of isocyanides with amines provides an efficient approach
for symmetric and unsymmetric functionalized carbodiimide derivative synthesis
under mild conditions.
T.-H. Zhu, S.-Y. Wang, Y.-Q. Tao, S.-J. Ji, Org. Lett.,
2015,
17, 1974-1977.
A mechanistically distinct approach achieves Suzuki-Miyaura-type
cross-couplings between alkyl iodides and aryl organoborons. This process
requires a copper catalyst but the activation of the alkyl electrophile is based
on the halogen-atom-transfer ability of α-aminoalkyl radicals to convert
secondary alkyl iodides into the corresponding alkyl radicals that then couple
with the boronate species.
Z. Zhang, B. Górski, D. Leonori, J. Am. Chem. Soc.,
2022, 144, 1758-1765.
A chiral (1S,2S)-cyclohexanediamine backbone salen-zirconium(IV)
complex as the catalyst enables a highly enantioselective α-hydroxylation of
β-keto esters using cumene hydroperoxide (CHP) as the oxidant to provide chiral
α-hydroxy β-keto esters in excellent yields and enantioselectivities. The
zirconium catalyst is recyclable and the reaction can be performed in gram scale.
F. Yang, J. Zhao, X. Tang, G. Zhou, W. Song, Q. Meng, Org. Lett.,
2017, 19, 448-451.
Nitroarenes react with anions of tert-butyl and cumyl
hydroperoxides in the presence of strong bases to form substituted o- and
p-nitrophenols. The reaction usually proceeds in high yields and is of
practical value as a method of synthesis and manufacturing of nitrophenols.
M. Makosza, K. Sienkiewicz, J. Org. Chem., 1998,
63, 4199-4208.