tert-Butyl hydroperoxide
Name Reactions
Recent Literature
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.
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.
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.
