Silyl alkyl peroxides

Alkyl hydroperoxides can form 2 1 adducts with DABCO. Both nitrogens of DABCO are involved and the resulting adduct contains 2 mol of hydroperoxide per mol of DABCO. Table 4 lists the silyl alkyl peroxides prepared using the DABCO-hydroperoxide adduct techniques. 

Silyl alkyl and silyl aryl peroxides 7 are prepared by reaction of alkyl, aryl or aralkyl hydroperoxides with halosilanes (equation 12). Such reactions are carried out in an inert solvent in the presence of an acid acceptor, such as pyridine, ammonia or a tertiary amine in ether or petroleum ether (Table 3) . ... 

TABLE 3. Silyl alkyl and aryl peroxides R R R Si—OOR 7 obtained according to equation 12... 

Alkyl(chloro)silyl peroxides 8 and alkyl alkoxysilyl peroxides are prepared by the alkyl hydroperoxidation of dichlorodiorganosilane (equations 13-15). 

Hydrosilylations of fluorine-containing alkenes are free radical reactions initiated by UV light or organic peroxides The direction of addition is the same as with fluonnated alkyl halides However, the reaction between hydrosilanes and fluorine-containing olefins catalyzed by platinum group metal complexes may result in bidirectional addition and/or formation of a vinylic silane, the latter by de hydrogenative silylation[/] The natures of both the silane and the catalyst affect the outcome of the reaction[7] A random selection of some typical new reactions of silanes are shown in Table 1 [1, 2, 3 4]... 

A diaryIprolinol silyl ether induces ee < 99% for aldehyde a-alkylation on 1,4-addition to acridinium salts. Computational chemistry has been used to explain stereoinduction by a family of iodooxazoline catalysts developed for enantioselective a-tosyloxylation of ketones by m-CPBA/TsOH. a-Benzoyloxylation of ketones (cyclohexanones and 1-indanones) by dibenzoyl peroxide occurs enantioselectively in the presence of a mixture of 9-amino-(9-deoxy)epi-dihydroquinidine and salicylic acid. ° The scope and limitations of asymmetric a-oxyacylation of cyclic ketones by chiral Ai-alkyl-O-acyl hydroxylamines have also been reported. ... 

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