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Rearrangement reactions silane

The kinetic data for the reaction of primary alkyl radicals (RCH2 ) with a variety of silanes are numerous and were obtained by applying the free-radical clock methodology. The term free-radical clock or timing device is used to describe a unimolecular radical reaction in a competitive study [2-4]. Three types of unimolecular reactions are used as clocks for the determination of rate constants for this class of reactions. The neophyl radical rearrangement (Reaction 3.1) has been used for the majority of the kinetic data, but the ring expansion rearrangement (Reaction 3.2) and the cyclization of 5-hexenyl radical (Reaction 3.3) have also been employed. [Pg.32]

Octa(phenyl)silsesquioxane is prepared by hydrolysis and condensation of phenyltrichlorosilane and the subsequent rearrangement reaction catalyzed by benzyltrimethylammonium hydroxide [22]. For further derivatization this precursor has to be activated, for example, by halogenation of the phenyl rings. This complex reaction sequence is necessary because halogenated precursors such as bromophenyl silanes of the type X3SiCgH4Br may be readily accessible from Grignard reactions between the benzene derivative and either SiCU or Si(OR)4, but the following hydrolysis and condensation step results in only low yields of... [Pg.7]

Extension of these processes to provide enantio-enriched products was successfully applied after desymmetrization of the starting materials. An example is shown below (Reaction 76), where silane-mediated xanthate deoxygenation-rearrangement-electrophile trapping afforded the conversion of (+)-94 to (+)-95 in 56% yield. ... [Pg.154]

There are, however, serious problems that must be overcome in the application of this reaction to synthesis. The product is a new carbocation that can react further. Repetitive addition to alkene molecules leads to polymerization. Indeed, this is the mechanism of acid-catalyzed polymerization of alkenes. There is also the possibility of rearrangement. A key requirement for adapting the reaction of carbocations with alkenes to the synthesis of small molecules is control of the reactivity of the newly formed carbocation intermediate. Synthetically useful carbocation-alkene reactions require a suitable termination step. We have already encountered one successful strategy in the reaction of alkenyl and allylic silanes and stannanes with electrophilic carbon (see Chapter 9). In those reactions, the silyl or stannyl substituent is eliminated and a stable alkene is formed. The increased reactivity of the silyl- and stannyl-substituted alkenes is also favorable to the synthetic utility of carbocation-alkene reactions because the reactants are more nucleophilic than the product alkenes. [Pg.862]

Normally, only a small stoichiometric excess (2-30 mol%) of silane is necessary to obtain good preparative yields of hydrocarbon products. However, because the capture of carbocation intermediates by silanes is a bimolecular occurrence, in cases where the intermediate may rearrange or undergo other unwanted side reactions such as cationic polymerization, it is sometimes necessary to use a large excess of silane in order to force the reduction to be competitive with alternative reaction pathways. An extreme case that illustrates this is the need for eight equivalents of triethylsilane in the reduction of benzyl alcohol to produce only a 40% yield of toluene the mass of the remainder of the starting alcohol is found to be consumed in the formation of oligomers by bimolecular Friedel-Crafts-type side reactions that compete with the capture of the carbocations by the silane.129... [Pg.12]

A mixture of exo- and endo-isomers of 5-methylbicylo[2.2.1]hept-2-ene is hydrogenated with the aid of five equivalents of triethylsilane and 13.1 equivalents of trifluoroacetic acid to produce a 45% yield of < <7o-2-methylbicylo[2.2.1] heptane (Eq. 71). The same product is formed in 37% yield after only five minutes. The remainder of the reaction products is a mixture of three isomeric secondary exo-methylbicylo[2.2.1]heptyl trifluoroacetates that remains inert to the reaction conditions. Use of triethylsilane-l-d gives the endo-2-methylbicylo-[2.2.1]heptane product with an exo-deuterium at the tertiary carbon position shared with the methyl group. This result reflects the nature of the internal carbocation rearrangements that precede capture by the silane.230... [Pg.37]

Dining preparation of tris(ketoximino)silanes, two violent explosions attributed to acid-catalysed exothermic rearrangement/decomposition reactions occurred. Although these silane derivatives can be distilled under reduced pressure, the presence of acidic impurities (e.g. 2-butanone oxime hydrochloride, produced during silane preparation) drastically reduces thermal stability. Iron(III) chloride at 500 ppm caused degradation to occur at 150°, and at 2% concentration violent decomposition set in at 50°C. [Pg.212]

Example The molecular ion of l,2-bis(trimethylsiloxy)benzene, m/z 254, undergoes methyl loss by Si-C bond cleavage as typically observed for silanes (Fig. 6.48). Rearrangement of the [M-CHb] ion then yields [Si(Me)3], m/z 73 (base peak). This is not an ortho elimination with concomitant H transfer as defined in the strict sense, but the observed reaction is still specific for the orthoisomer. [190,203] In the spectra of the meta- and para-isomers the [Si(Me)3] ion is of lower abundance, the [M-CHb] ion representing the base peak in their spectra. Moreover, the m/z 73 ion is then generated directly from the molecular ion which is clearly different from the two-step pathway of the ortho-isomer. [Pg.307]

The concept of this method is illustrated in Scheme 3.1, where the clock reaction (U R ) is the unimolecular radical rearrangement with a known rate constant ( r)- The rate constant for the H atom abstraction from RsSiH by a primary alkyl radical U can be obtained, provided that conditions are found in which the unrearranged radical U is partitioned between the two reaction channels, i.e., the reaction with RsSiH and the rearrangement to R. At the end of the reaction, the yields of unrearranged (UH) and rearranged (RH) products can be determined by GC or NMR analysis. Under pseudo-first-order conditions of silane concentration, the following relation holds UH/RH = (A H/A r)[R3SiH]. A number of reviews describe the radical clock approach in detail [3,4]. [Pg.32]

The intramolecular addition of silyl radicals to aromatic rings has also attracted some attention. Early work on the silyl radical obtained by the reaction of silanes 41 with thermally generated t-BuO radicals at 135 °C showed the formation of rearranged products only for = 3 or 4, whereas for = 1, 2, 5, and 6 no rearrangement took place [20],... [Pg.129]

This silylperoxyl radical undergoes an unusual rearrangement to 13 followed by a 1,2-shift of the MesSi group to give 14. Hydrogen abstraction from the silane by radical 14 gives the desired product and another silyl radical 11, thus completing the cycle of this chain reaction. [Pg.193]


See other pages where Rearrangement reactions silane is mentioned: [Pg.410]    [Pg.399]    [Pg.274]    [Pg.226]    [Pg.247]    [Pg.34]    [Pg.202]    [Pg.360]    [Pg.177]    [Pg.733]    [Pg.93]    [Pg.23]    [Pg.31]    [Pg.287]    [Pg.22]    [Pg.154]    [Pg.148]    [Pg.162]    [Pg.1209]    [Pg.431]    [Pg.556]    [Pg.25]    [Pg.240]    [Pg.132]    [Pg.193]    [Pg.246]   
See also in sourсe #XX -- [ Pg.399 , Pg.400 ]




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