tert-Butyl hydroperoxide

Name Reactions

Sharpless Epoxidation

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Recent Literature

Various aromatic, aliphatic and conjugated alcohols were transformed into the corresponding carboxylic acids and ketones in good yields with aq 70% t-BuOOH in the presence of catalytic amounts of bismuth(III) oxide. This method possesses does not involve cumbersome work-up, exhibits chemoselectivity and proceeds under ambient conditions. The overall method is green.
P. Malik, D. Chakraborty, Synthesis, 2010, 3736-3740.

The cationic complex [(pymox-Me₂)RuCl₂]⁺BF₄^- is a highly effective catalyst for the C-H bond oxidation of aryl alkanes in water using tert-butyl hydroperoxide as oxidant to yield various aryl ketones at room temperature in water as solvent. A solvent-caged oxygen rebounding mechanism via a Ru(IV)-oxo intermediate species is suggested.
C. S. Yi, K.-H. Kwon, D. W. Lee, Org. Lett., 2009, 11, 1567-1569.

The bismuth and picolinic acid-catalyzed oxidation of alkyl arenes with tert-butyl hydroperoxide in pyridine and acetic acid gave benzylic ketones in good yields. Alternatively, oxidation of methyl arenes gave the corresponding substituted benzoic acids. A radical mechanism is discussed.
Y. Bonvin, E. Callens, I. Larrosa, D. A. Henderson, J. Oldham, A. J. Burton, A. G. M. Barrett, Org. Lett., 2005, 7, 4549-4552.

Utilizing the rapidly synthesized Quinox ligand and commercially available aqueous TBHP, a Wacker-type oxidation efficiently converts even traditionally challenging substrates such as protected allylic alcohols to the corresponding oxidized products. Enantioenriched substrates undergo oxidation with complete retention of enantiomeric excess.
B. W. Michel, A. M. Camelio, C. N. Cornell, M. S. Sigman, J. Am. Chem. Soc., 2009, 131, 6076-6077.

A ruthenium-catalyzed oxidation of alkenes allows an efficient route to α-diketones using TBHP as an oxidant, is highly functional group tolerant and practically convenient, requires no additional ligand, and operates under mild conditions with short reaction times. Based upon experimental observations, a plausible mechanism is proposed.
S. Chen, Z. Liu, E. Shi, L. Chen, W. Wei, H. Li, Y. Cheng, X. Wan, Org. Lett., 2011, 13, 2274-2277.

Dirhodium(II) caprolactamate effectively catalyzes the allylic oxidation of a variety of olefins and enones with tert-butyl hydroperoxide as terminal oxidant. The reaction is completely selective, tolerant of air and moisture, and can be performed with as little as 0.1 mol % catalyst in minutes.
A. E. Lurain, A. Maestri, A. R. Kelli, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc., 2004, 126, 13622-13623.

A new and simple method is described for the one-step oxidation of α,β-enones to 1,4-enediones in good yields using t-butylhydroperoxide as stoichiometric oxidant and 20% Pd(OH)₂ on carbon as catalyst. The same reagents have been used to convert ethylene ketals of α,β-enones to the corresponding monoethylene ketals of 1,4-enediones. The mechanism is discussed.
J.-Q. Yu, E. J. Corey, J. Am. Chem. Soc., 2003, 125, 3232-3233.

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, use of aqueous tert-butyl hydroperoxide (TBHP) instead of anhydrous TBHP as an achiral oxidant, 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.

A mild and efficient oxidative amidation of aldehydes uses amine HCl salts and tert-butyl hydroperoxide as an oxidant in the presence of a copper catalyst.
W.-J. Yoo, C.-J. Li, J. Am. Chem. Soc., 2006, 128, 13064-13065.

The catalytic asymmetric addition of alkyl groups to ketones under highly concentrated and solvent-free conditions permits reduction in catalyst loading by a factor of 2- to 40-fold compared with standard reaction conditions employing toluene and hexanes. Using cyclic conjugated enones, solvent-free asymmetric addition followed by a diastereoselective epoxidation using 5.5 M decane solution of tert-butyl hydroperoxide generated epoxy alcohols.
S.-J. Jeon, H. Li, P. J. Walsh, J. Am. Chem. Soc., 2005, 127, 16416-16425.

A catalytic asymmetric epoxidation reaction of various α,β-unsaturated esters via a conjugate addition of an oxidant using an yttirium-chiral biphenyldiol catalyst yielded the corresponding α,β-epoxy esters in up to 97% yield and 99% ee.
H. Kakei, R. Tsuji, T. Ohshima, M. Shibasaki, J. Am. Chem. Soc., 2005, 127, 8962-8963.

A gold(I)-catalyzed oxidative cleavage of alkenes with tert-butyl hydrogenperoxide (TBHP) as the oxidant in the presence of neocuproine afforded ketones or aldehydes as products.
D. Xing, B. Guan, G. Cai, Z. Fang, L. Yang, Z. Shi, Org. Lett., 2006, 8, 693-696.

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.

Stereodefined enol derivatives of aldehydes are prepared from terminal alkynes through Cp₂ZrCl₂-catalyzed methylalumination and subsequent oxygenation with peroxyzinc species and electrophilic trapping with carboxylic anydrides. The tandem carbometalation/oxygenation tolerates free and protected alcohols, heterocycles, olefins, and nitriles.
J. R. DeBergh, K. M. Spivey, J. M. Ready, J. Am. Chem. Soc., 2008, 130, 7828-7829.

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.

A simple and effective copper-catalyzed oxidative cross-coupling of dimethylanilines with alkynes in the presence of tert-BuOOH allows the construction of propargylamines via a combination of sp³ C-H bond and sp C-H bond activations followed by C-C bond formation.
Z. Li, C.-J. Li, J. Am. Chem. Soc., 2004, 126, 11810-11811.

A copper-catalyzed amidation of allylic and benzylic C-H is applicable to the coupling of a diverse set of hydrocarbon species with aryl, heteroaryl, and alkyl sulfonamides and is tolerant of a variety of functional groups.
G. Pelletier, D. A. Powell, Org. Lett., 2006, 8, 6031-6034.

A facile one-pot, transition-metal-free process enables the synthesis of various polysubstituted oxazoles via t-BuOOH/I₂-mediated domino oxidative cyclization from readily available starting materials under mild conditions.
H. Jiang, H. Huang, H. Cao, C. Qi, Org. Lett., 2010, 12, 5561-5563.

In a practical and simple synthesis of 2,5-disubstituted oxazoles via an iodine-catalyzed tandem oxidative cyclization, a wide range of common commercial aromatic aldehydes can be used as reaction substrates, which displayed excellent functional group compatibility.
C. Wan, L. Gao, Q. Wang, J. Zhang, Z. Wang, Org. Lett., 2010, 12, 3902-9305.

A highly efficient copper-catalyzed tandem oxidative cyclization gives polysubstituted oxazoles from readily available starting materials under mild conditions. This is an attractive alternative method for the synthesis of oxazole derivatives.
C. Wang, J. Zhang, S. Wang, J. Fan, Z. Wang, Org. Lett., 2010, 12, 2338-2341.

A facile approach allows the synthesis of 2-phenylquinazolines via a tandem reaction following sp³ C-H functionalization. Twenty-five examples of 2-phenylquinazolines were obtained from easily available 2-aminobenzophenones and benzylic amines with good to excellent yields.
J. Zhang, D. Zhu, C. Yu, C. Wan, Z. Wang, Org. Lett., 2010, 12, 2841-2843.

A facile and efficient method for the synthesis of 2-phenylquinazolines from 2-aminobenzophenones and benzylamines us catalyzed by ceric ammonium nitrate (CAN)-TBHP in acetonitrile. The corresponding 2-phenylquinazolines were obtained in good to excellent yields.
K. Karnakar, J. Shangkar, S. N. Murthy, K. Ramesch, Y. V. D. Nageshwar, Synlett, 2011, 1089-1096.

Aqueous tert-butyl hydroperoxide (70%) is an inexpensive reagent for the regioselective and chemoselective deprotection of terminal acetonide groups. Various acetonide derivatives furnish the corresponding deprotected diols in good yields, while a large number of acid labile protecting functional groups and other functional moieties were found to be unaffected under the conditions.
M. R. Maddani, K. R. Prabhu, Synlett, 2011, 821-825.