Hydroperoxides, in epoxidations

Although the proposals advancing 4 and 6 as intermediates in the epoxidation explain most of the experimental data reported to date, there are a few remaining enigmas such as the reversal of enantioselectivity which accompanies the use of primary amide analogs of tartrates (Table 3) and when ferf-butyl hydroperoxide is replaced by triphenylmethyl hydroperoxide in epoxidations employing catalyst 840. 

As stated earlier, HoO, is not as effective as organic hydroperoxides in epoxidation with Mo complexes. Nevertheless, the subject has been studied, and again... 

In light of the previous discussions, it would be instructive to compare the behavior of enantiomerically pure allylic alcohol 12 in epoxidation reactions without and with the asymmetric titanium-tartrate catalyst (see Scheme 2). When 12 is exposed to the combined action of titanium tetraisopropoxide and tert-butyl hydroperoxide in the absence of the enantiomerically pure tartrate ligand, a 2.3 1 mixture of a- and /(-epoxy alcohol diastereoisomers is produced in favor of a-13. This ratio reflects the inherent diasteieo-facial preference of 12 (substrate-control) for a-attack. In a different experiment, it was found that SAE of achiral allylic alcohol 15 with the (+)-diethyl tartrate [(+)-DET] ligand produces a 99 1 mixture of /(- and a-epoxy alcohol enantiomers in favor of / -16 (98% ee). 

A potentially powerful probe for sorting out the contribution of hydroperoxide-dependent and mixed-function oxidase-dependent polycyclic hydrocarbon oxidation is stereochemistry. Figure 9 summarizes the stereochemical differences in epoxidation of ( )-BP-7,8-dihydrodiol by hydroperoxide-dependent and mixed-function oxidase-dependent pathways (31,55,56). The (-)-enantiomer of BP-7,8-dihydrodiol is converted primarily to the (+)-anti-diol epoxide by both pathways whereas the (+)-enantiomer of BP-7,8-dihydrodiol is converted primarily to the (-)-anti-diol epoxide by hydroperoxide-dependent oxidation and to the (+)-syn-diol epoxide by mixed-function oxidases. The stereochemical course of oxidation by cytochrome P-450 isoenzymes was first elucidated for the methycholanthrene-inducible form but we have detected the same stereochemical profile using rat liver microsomes from control, phenobarbital-, or methyl-cholanthrene-induced animals (32). The only difference between the microsomal preparations is the rate of oxidation. 

The reaction of olefin epoxidation by peracids was discovered by Prilezhaev [235]. The first observation concerning catalytic olefin epoxidation was made in 1950 by Hawkins [236]. He discovered oxide formation from cyclohexene and 1-octane during the decomposition of cumyl hydroperoxide in the medium of these hydrocarbons in the presence of vanadium pentaoxide. From 1963 to 1965, the Halcon Co. developed and patented the process of preparation of propylene oxide and styrene from propylene and ethylbenzene in which the key stage is the catalytic epoxidation of propylene by ethylbenzene hydroperoxide [237,238]. In 1965, Indictor and Brill [239] published studies on the epoxidation of several olefins by 1,1-dimethylethyl hydroperoxide catalyzed by acetylacetonates of several metals. They observed the high yield of oxide (close to 100% with respect to hydroperoxide) for catalysis by molybdenum, vanadium, and chromium acetylacetonates. The low yield of oxide (15-28%) was observed in the case of catalysis by manganese, cobalt, iron, and copper acetylacetonates. The further studies showed that molybdenum, vanadium, and... 

The health impairing and toxic elfects of oxidation of lipids are due to loss of vitamins, polyenoic fatty acids, and other nutritionally essential components formation of radicals, hydroperoxides, aldehydes, epoxides, dimers, and polymers and participation of the secondary products in initiation of oxidation of proteins and in the Maillard reaction. Dilferent oxysterols have been shown in vitro and in vivo to have atherogenic, mutagenic, carcinogenic, angiotoxic, and cytotoxic properties, as well as the ability to inhibit cholesterol synthesis (Tai et ah, 1999 Wpsowicz, 2002). 

A broad spectrum of chemical reactions can be catalyzed by enzymes Hydrolysis, esterification, isomerization, addition and elimination, alkylation and dealkylation, halogenation and dehalogenation, and oxidation and reduction. The last reactions are catalyzed by redox enzymes, which are classified as oxidoreductases and divided into four categories according to the oxidant they utilize and the reactions they catalyze 1) dehydrogenases (reductases), 2) oxidases, 3) oxygenases (mono- and dioxygenases), and 4) peroxidases. The latter enzymes have received extensive attention in the last years as bio catalysts for synthetic applications. Peroxidases catalyze the oxidation of aromatic compounds, oxidation of heteroatom compounds, epoxidation, and the enantio-selective reduction of racemic hydroperoxides. In this article, a short overview... 

AUyl transfer reactions, 73, 1 Allylic alcohols, synthesis from epoxides, 29, 3 by Wittig rearrangement, 46, 2 Allylic and benzylic carbanions, heteroatom-substituted, 27, 1 Allylic hydroperoxides, in... 

Although hydrogen peroxide and aUcyl hydroperoxides in general are not snfliciently reactive to epoxidize alkenes, there are some exceptions. Experimental observations show that direct olefin epoxidation by H2O2, which is extremely sluggish otherwise, occurs in fluorinated alcohol (RfOH) solutions under mild conditions requiring no additional... 

Besides the chiral, secondary hydroperoxides employed by Adam and coworkers and the tertiary hydroperoxide used by Seebach, the optically active carbohydrate hydroperoxides 72, 93 and 94 have been tested by Taylor and coworkers in epoxidation reactions of the quinones 95 under basic conditions (Scheme 41). The yields of the corresponding epoxides 96 that were obtained with this type of oxidant varied from 33 to 83% and the enantioselectivities were moderate and in some cases good (23 to 82%), depending... 

The anthers fonnd that the confignration of the anomeric C-atom, to which the hydroper-oxy gronp is bonnd, determines the absolnte confignration of the epoxide formed. Remarkably, the aUylic alcohol 142p, which conld not be epoxidized nnder Sharpless conditions, was oxidized by the carbohydrate hydroperoxides in combination with Ti(OPr-i)4, albeit with low ee (11%). 

SCHEME 64. Titanium-catalyzed asymmetric epoxidation of aUyhc alcohols with secondary chiral hydroperoxides in the presence of diol additives... 

The use of a chiral hydroperoxide as oxidant in the asymmetric Baeyer-ViUiger reaction was also described by Aoki and Seebach, who tested the asymmetric indnction of their TADOOH hydroperoxide in this kind of reaction . Besides epoxidation and snlfoxidation, for which they found high enantioselectivities with TADOOH (60), this oxidant is also able to induce high asymmetry in Baeyer-ViUiger oxidations of racemic cyclobntanone derivatives in the presence of DBU as a base and LiCl as additive (Scheme 174). The yields and ee values (in parentheses) of ketones and lactones are given in Scheme 174 as... 

The elution factors in normal-phase TLC and RP-HPLC, using a fixed set of chromatographic parameters, were determined for a series of saturated triacylglycerides with TCN from C30 to Ceo, serving as reference compounds and various oxidation derivatives of analogous unsaturated triglycerides, including hydroperoxides, peroxides, epoxides, core aldehydes and their DNP derivatives. From these measurements, a series of incremental... 

These complexes are effective catalysts in epoxidation reactions with H2O2 and alkyl hydroperoxides. Several detailed mechanistic studies have been carried out in particular, it has been shown that, when the alkyl chain contains a double bond, no autoepoxidation is observed both in the solid state and in solution. Nevertheless, if f-BuOOH is added, the epoxidation of the olefinic moiety immediately takes place. Therefore, it has been suggested that these complexes are not the active species in the oxygen transfer step to the substrate, but they behave as catalysts for the primary peroxidic oxidant. On the basis of kinetic, spectroscopic and theoretical studies, the authors provided a mechanism, whose key steps are sketched in Scheme 12. In this context a major role appears to be played by the fluxionality of the particular ligands used . ... 

Of the many studies of the autoxidation of butenes, few (5,11) have emphasized methyl vinyl ketone and methyl vinyl carbinol as major products. In the cumene hydroperoxide-initiated oxidation of 1-butene at 105°C. with 60 atm. of air, Chernyak (5) reported an average hourly rate of production of these two products approximately equal to the combined rates of formation of hydroperoxide and epoxide. The reported rates for hydroperoxide plus vinyl ketone and alcohol indicate that 60% of the products occur by abstraction, in agreement with Van Sickle (17). 

The ligand (S)-N-methylprolinol was used in a 2 1 molar ratio to the Mo02(acac)2 catalyst (1 mol % on the allylic alcohol (43) in the epoxidation of 3-methyl-2-buten-l-ol (43) with cumene hydroperoxide in cyclohexane solvent. 

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