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).
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.