Oxidants tert-butylhydroperoxide

Jewell, S.A., DiMonte, D., Richelmi, P., Bellomo, G. and Orrenius, S. (1986). tert-Butylhydroperoxide-induced toxicity in isolated hepatocytes contribution of thiol oxidation and lipid peroxidation. J. Biochem. Toxicol. 1, 13-22. 

The formation of methylperoxy intermediates—i.e., the product of a formal insertion of O2 into the metal-methyl bond—was substantiated by the observation of epoxidation of allylic alkoxides (Scheme 6), in analogy to the proposed mechanism for the Sharpless epoxidation utilizing tert-butylhydroperoxide (TBHP). A similar oxygen atom transfer from a coordinated alkylperoxide to olefin was also postulated for the epoxidation of olefins with TBHP catalyzed by Cp Mo(0)2Cl [31]. The use of organomolybdenum oxides in olefin epoxidafion cafalysis (albeit not with O2) has recently been reviewed [32]. 

The oxidation to methyl ketones without cleavage of the double bond was reported recently for a palladium NHC complex [108]. When the authors used the previously described catalyst 13 in THF with dioxygen for the oxidation of styrene they found that together with the phenylmethylketone a significant amount of y-butyrolactone was formed. Analysis of the mechanism led to the conclusion that THF is oxidized to a hydroperoxide species which is the real oxidant. They therefore tried tert-butylhydroperoxide (TBHP) and found immediate conversion without any induction period. Optimized conditions include 0.75 mol % of the previously described dimeric complex... 

Liquid-Phase Oxidation Reactions with tert-Butylhydroperoxide or Other Oxidants Catalyzed bv... 

A Ni-containing sandwich complex, Nij(a-PW90j9)2, is a better catalyst than PWn(M)C>39 (M = Co, Mn) for the formation of N-alkylacetamide from adamantane and isobutane with tert-butylhydroperoxide as the oxidant (323). 

For oxidation add 100 equivalents of dry tert -butylhydroperoxide solution (5.5 M in decan see Note 20), close the tube and incubate at room temperature for 90 min by gentle shaking. 

For the first time, catalytic activity of lanthanide isopropoxides was detected in the TBHP (tert-butylhydroperoxide) assisted oxidation of allylic alcohols to epoxyalcohols (Eq. 26) [231], For example epoxy geraniol was obtained in up to 96% yield by using YbfOiPr in the presence of molecular sieves (4 A) [232]. 

Sohn, J.H., Han, K.L., Choo, J.H. and Hwang, J.K. (2007) Macelignan protects HepG2 cells against tert-butylhydroperoxide-induced oxidative damage. 1. Biofactors 29(1), 1-10. 

It has recently been found42 that Au/C and Au/graphite catalysts are effective for the aerobic oxidation of other alkenes at 353 K small amounts of either hydrogen peroxide or tert-butylhydroperoxide ( BuOOH) are needed as oxygen chain initiators. The products of the reactions of cyclohexene,... 

The epoxidation of propene with tert-butylhydroperoxide (TBHP) or ethylbenzene hydroperoxide (EBHP), for example, accounts for more than one million tons of propene oxide production on an annual basis (Fig. 4.19). 

Ruthenium(II) complexes may also be used to oxidize N-Boc hydroxylamine in the presence of tert-butylhydroperoxide (TBHP) to the corresponding nitroso dieno-phile, which is subsequently trapped by cyclohexa-1,3-diene to give the hetero Diels-Alder adduct (Entry 1, Scheme 10.26) [51]. A triphenylphosphine oxide-stabilized ruthenium(IV) oxo-complex was found to be the catalytically active species. Use of a chiral bidentate bis-phosphine-derived ruthenium ligand (BINAP or PROPHOS) result in very low asymmetric induction (8 and 11%) (Entry 2, Scheme 10.26). The low level of asymmetric induction is explained by the reaction conditions (in-situ oxidation) that failed to produce discrete, stable diastereomerically pure mthenium complexes. It is shown that ruthenium(II) salen complexes also catalyze the oxidation of N-Boc-hydroxylamine in the presence of TBHP, to give the N-Boc-nitroso compound which can be efficiently trapped with a range of dienes from cyclohepta-1,3-diene (1 h, r.t., CH2CI2, 71%) to 9,10-dimethylanthracene (96 h, r.t., CH2CI2,... 

Baldwin and Walker [99] have pointed out that, from kinetic considerations, surface reactions of alkylperoxy radicals cannot play a significant role except at very low overall rates of reaction and conclude that it is more likely that surface destruction of relatively stable intermediates such as the alkyl hydroperoxides or hydrogen peroxide are the main cause of surface effects in hydrocarbon oxidation. Luckett and Pollard [68, 134] have provided evidence, which suggests that the surface destruction of tert-butylhydroperoxide is indeed important during the oxidation of isobutane below ca. 320 °C. Since isobutene and acetone are known products of the decomposition of tert-butylhydroperoxide, it is clear that many of the foregoing results can be explained in these terms, but if this is the predominant heterogeneous reaction the yield of acetone would be... 

Good conversion (reaching a maximum of ca 87% at 378 K) and high selectivity (ca 78% at 348 K) were observed (Fig. 21.1) and the performance of the single-site Mn AlPO-5 catalyst was superior to that of TS-1, both in terms of activity and selectivity. The use of APB in conjunction with the Mn AlPO-5 catalyst resulted in a better selectivity for the (desired) nicotinic acid when compared with other conventional oxidants such as H O, PAA or tert-butylhydroperoxide (TBHP). 

Acalypha wilkesiana van macafeana hort. Din et al. [236] studied the properties of Acalypha wilkesiana var. macafeana hort, used to heal wounds in Malaysian traditional medicine. Acalypha wilkesiana ar. macafeana hort. protected human hepatocellular liver carcinoma (HepG2) cells exposed to tert-butylhydroperoxide, and protected cells against oxidative injuries, showing potent antioxidant and cytoprotective activities. These effects might be exerted bygeraniin [236],... 

UTD-1 may have catalytic properties such as those observed with the commercially sucsessfiil titanium silicahte TS-1 catalyst which is effective for alkane and alkene o ddation as well as phenol hydroxylation in the presence of hydrogen peroxide [8]. The large pore nature of Ti-UTD-1 should allow the reaction of large substrates such as 2,6-di-tert-butylphenol as well as the use of oxidants such as tert-butylhydroperoxide (t-BHP) which are too large for the medium pore TS-1 zeolite. Ti-UTD-1 offers an opportunity to examine reactivity in pore space greater than Ti-beta but less than the mesoporous Ti-MCM-41 type molecular sieves. In the present study results for the peroxide based oxidation of cyclohexane, cyclohexene and 2,6-di-tert-butylphenol will be presented. 

Sharpless and co-workers have devised an enantiospe-cific oxidation of allylic alcohols to the epoxides using tert-butylhydroperoxide in the presence of titanium(TV) iso-propoxide and dialkyl tartrates (10.45).103... 

Oxidation of hydrocarbons in zeolites with blue light gives improved selectivity.442 Isobutane can be converted to tert-butylhydroperoxide with 98% selectivity. Benzalde-hyde is produced from toluene, acrolein from propylene, and acetone from propane. 

Wird die Oxidation mit tert.-Butylhydroperoxid unter neutralen Bedingungen in Ethanol durch-gefiihrt, erfoigt C,C-Verkniipfung iiber die 4-Position1521 (radikalischer Reaktionsverlauf)-... 

The allylic 4a-methyl group can be oxidized with Se02-catalyzed tert-butylhydroperoxide to a 4a-hydroxy analogue (44). 

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