Peroxide reaction with alkenes

Formaldehyde, benzaldehyde and aniline react violently with 90% performic acid (Ref 1). An unspecified organic compd was added to the acid, and soon after the initial vigorous reaction had subsided, the mixt expld violently (Ref 3). Reaction with alkenes is vigorously exothermic, and adequate cooling is necessary. Reactions with performic acid can be more safely accomplished by the slow addition of hydrogen peroxide to a soln of the compd in formic acid (Ref 4)... 

Tertiary alkylhydroperoxides are used most often as oxidizing agents with alkenes since primary or secondary alkylhydroperoxides are susceptible to rearrangement and decomposition. Alkylhydroperoxides are relatively soluble in organic solvents, are more stable, and are easier to handle than hydrogen peroxide.256 Both TBHP and cumyl hydroperoxide are commercially available and widely used. As with hydrogen peroxide, reaction of alkenes with hydroperoxides usually requires transition metal catalysts in order to form... 

The hydroboration reaction with alkenes to produce alkylboranes (sec. 5.2) proceeds by a four-center transition state rather than a cationic intermediate. The regiochemistry of the final alkylborane product is controlled by the nonbonded steric interactions of the groups attached to boron (in this case sec-isoamyl from the disiamylborane) and the groups on the alkene. Oxidation with basic hydrogen peroxide converts the borane to the anti-Markovnikov alcohol (2). The difference in regiochemistry between 1 and 2 arose because the mechanism for generating each relied on difference factors. 

Osmium tetroxide can undergo reaction with alkenes to form a cyclic osmate, which in the presence of hydrogen peroxide results in a glycol (diol). Hydrogen peroxide oxidizes the osmium back to osmium tetroxide, while hydrolyzing the cyclic osmate to glycol. The predominant product is a syn addition product. 

Using spectroscopic methods, it was established that peroxymonocarbonate (HC04 ) is formed on mixing hydrogen peroxide and bicarbonate [57]. In the absence of the metal catalyst, the oxidizing power of the peroxymonocarbonate formed in situ with respect to its reaction with alkenes was demonstrated to be moderate. In the initial reaction setup, this MnS04hydrogen peroxide (10 equiv.) for efficient epoxide formation. 

Singlet Oxygen.—Singlet oxygen reacts with dienes to give e do-peroxides and with alkenes to give allylic hydroperoxides or dioxetans. " The mechanism of the latter reaction is still under investigation. The use of these reactions in natural products synthesis has been comprehensively reviewed, "— " and attention will be concentrated on recent work. 

Among the hydrogen halides only hydrogen bromide reacts with alkenes by both electrophilic and free radical addition mechanisms Hydrogen iodide and hydrogen chlo ride always add to alkenes by electrophilic addition and follow Markovmkov s rule Hydrogen bromide normally reacts by electrophilic addition but if peroxides are pres ent or if the reaction is initiated photochemically the free radical mechanism is followed... 

The reaction is particularly effective with alkenes with electron-attracting substituents such as diethyl maleate. When the reaction is conducted thermally with a peroxide initiator at 160°C, the product mixture is much more complex ... 

In addition to the oxymercuration method, which yields the Markovnikov product, a complementary method that yields the non-Markovnikov product is also useful. Discovered in 1959 by H. C. Brown and cailed hydroboration, the reaction involves addition of a B-H bond of borane, BH3, to an alkene to yield an organoborane intermediate, RBH2. Oxidation of the organoborane by reaction with basic hydrogen peroxide, H2O2, then gives an alcohol. For example ... 

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